Liquid crystal compounds, liquid crystal compostions containing the compounds, and liquid crystal display devices made by using the compositions

ABSTRACT

The invention is to provide liquid crystalline compounds which have a low viscosity, high negative dielectric anisotropy, high resistivity, and high voltage holding ratio, and are stable against heat and ultraviolet light; to provide liquid crystal compositions comprising the liquid crystalline compound; and to provide liquid crystal display devices using the liquid crystal composition therein; 
     the liquid crystalline compound is expressed by the general formula (1)                    
     wherein R 1  and Y 1  represent an alkyl group having 1 to 20 carbon atoms; X 1 , X 2 , and X 3  independently represent single bond, 1,2-ethylene group, vinylene group, —COO—, —CF 2 O—, or —OCF 2 —; ring A 1 , ring A 2 , ring A 3 , and ring A 4  independently represent trans-1,4-cyclohexylene, or 1,4-phenylene hydrogen atom on the ring may be replaced by fluorine atom or chlorine atom provided that at least one of ring A 2 , ring A 3 , and ring A 4  represents 2,3-difluoro-1,4-phenylene; m and n are 0 or 1, and each element which constitutes this compound may be replaced by its isotope.

This application is a 371 of PCT/JP97/01048, filed Feb. 27, 1997.

TECHNICAL FIELD

The present invention relates to novel liquid crystalline compounds which make liquid crystal compositions principally for it twist nematic (TN) display mode, super twist nematic (STN) display mode, or thin film transistor (TFT) display mode develop preferable physical properties, to liquid crystal compositions comprising the liquid crystalline compound and having preferable physical properties, and to liquid crystal display devices using the liquid crystal composition therein.

BACKGROUND ART

Liquid crystal display devices utilize optical anisotropy and dielectric anisotropy of liquid crystal substances. The liquid crystal display devices are widely used in tabletop calculators, word processors, and television sets, including watches, and demand for the display devices is in a trend to increase year by year. Liquid crystal phase exists between solid phase and liquid phase, and is divided broadly into nematic phase, smectic phase, and cholesteric phase. Among them, nematic phase is most widely employed for display devices at present. On the other hand, while many display modes were devised up to date, three types of twist nematic (TN) mode, super twist nematic (STN) mode, and thin film transistor (TFT) mode have now become main currents. Properties required of liquid crystal substances (liquid crystalline compounds) for these various liquid crystal display devices are different depending on their uses, but any of the liquid crystal substances is required to be stable against outside environmental factors such as moisture, air, heat, and light; to exhibit liquid crystal phase at a temperature range as wide as possible with room temperature being its center; to be in a low viscosity; and to have a low driving voltage. However, no liquid crystal substances which satisfy such requirements at the same time by a single compound have been found.

With respect to liquid crystal substances used for liquid crystal display devices, it is an actual circumstance that several kind or several tens kind of liquid crystalline compounds, and further several kind of liquid non-crystalline compounds when necessary, are usually mixed to produce liquid crystal compositions and used for display devices, in order to adjust such physical properties as dielectric anisotropy (Δε), optical anisotropy (Δn), viscosity, and elastic constant ratio K₃₃/K₁₁ (K₃₃: bend elastic constant, K₁₁: splay elastic constant) of liquid crystal compositions to most suitable ones required of each display device. Accordingly, liquid crystalline compounds are required to be excellent in miscibility with other liquid crystal compounds, and recently in particular required to be excellent in the miscibility even at low temperatures from the requirement of being used in various environments.

Meanwhile, active matrix mode, especially thin film transistor (TFT) mode is extensively adopted in recent years as display mode, for example, for television sets and viewfinders from the aspect of display performances such as contrast, display capacity, and response time. Also, STN mode which has a large display capacity and display devices of which can be produced by comparatively simpler methods and at a lower cost than those of active matrix mode from the structural factor of display devices is largely adopted in displays, for example, for personal computers.

Recent development in these fields is being progressed while placing stress on

(a) downsizing of liquid crystal display devices into a portable size as shown by the development of small size TV sets and notebook size personal computers both of which are characterized by being in small size, light, and thus portable; and

(b) production of liquid crystalline compounds and liquid crystal compositions having a low driving voltage, that is, a low threshold voltage from the viewpoint of withstand voltage of IC, in the aspect of liquid crystal material.

It is known that threshold voltage (V_(th)) can be expressed by the following equation (H. J. Deuling et al., Mol. Cryst. Liq. Cryst., 27 (1975) 81):

V _(th)=π(K/ε ₀Δε)^(½)

In the equation described above, K is an elastic constant and ε₀ is a dielectric constant in vacuum. As will be seen from this equation, two methods, that is, a method of increasing dielectric anisotropy (Δε) and a method of lowering elastic constant can be considered to lower the threshold voltage. However, since actual control of elastic constant is very difficult, it is an actual situation that liquid crystal materials having a high dielectric anisotropy (Δε) are ordinarily used to cope with the requirements. With the facts described above for a background, development of liquid crystalline compounds having a high dielectric anisotropy (Δε) has actively been conducted.

Almost all liquid crystal compositions currently used in display devices for TFT mode are composed of fluorine type liquid crystal materials. This is because (i) a high voltage holding ratio (V.H.R.) is required in TFT mode from the viewpoint of construction of the devices, (ii) the materials have to be small in the temperature dependency, and (iii) materials other than fluorine type can not meet these requirements. As fluorine type materials for low voltage, the following compounds are heretofore disclosed:

in the structural formula described above, R represents an alkyl group.

Whereas it is reported that either compounds (a) and (b) have several fluorine atoms at a terminal of the molecule and exhibit a high dielectric anisotropy, it is known that their clearing point (NI point) is low and viscosity is a comparatively high. Among the persons skilled in the art, it is empirically known that there are inversely proportional and direct proportional relations between the number of substituted fluorine atom and the clearing point, and between the number of substituted fluorine atom and the viscosity, respectively, although it is not simple. Accordingly, it is difficult to attain the required clearing point and viscosity (response speed) when liquid crystal compositions are produced only a series of these compounds. With the object of offsetting this defect, a viscosity decreasing agent represented by the following compounds is usually added in liquid crystal compositions.

in the structural formula described above, R and R′ represent an alkyl group.

Whereas compounds (c) have a comparatively low viscosity, their clearing point is not sufficiently high to offsetting the low clearing point of liquid crystal compositions comprising the liquid crystalline compounds for low voltage described above. In order to meet the requirement, a comparatively large amount is necessary to be added, but characteristics of liquid crystal compositions are lost in this case. Accordingly, compounds (c) are unsuitable as material to solve the problems described above. Whereas compounds (d) have a sufficiently high clearing point, their viscosity is remarkably high since they have a four ring structure. Thus, the increase in the viscosity is unavoidable when the compounds (d) are added in liquid crystal compositions. Besides, since compounds (d) themselves have smectic phase, when liquid crystal compositions prepared by adding the compounds were left at a low temperature, smectic phase some times develops in the liquid crystal compositions. Accordingly, compounds (d) are unsuitable to solve the problems described above, either. Further, since any one of compounds (c) and (d) has an extremely low dielectric anisotropy value, when it is added to liquid crystal compositions for low voltage having a large dielectric anisotropy value as described above, the compound considerably lower the dielectric anisotropy of the liquid crystal compositions. As the result, the threshold voltage of the compositions raise, and thus, the compound is not preferable to solve the problems.

In the meantime, researches to overcome narrow viewing angle which is only one defect of liquid crystal panel of TFT display mode were actively conducted recent years, and many results of the researches are reported at lectures in academic society and disclosed in patent publications. As an example of the step for the improvement, the following method is disclosed. For instance, in Laid-open Japanese Patent Publication Nos. Hei 4-229828 and Hei 4-258923, a method is disclosed in which the viewing angle is improved by disposing a phase difference film between a pair of polarizing plates and a TN type liquid crystal cell. In Laid-open Japanese Patent Publication Nos. Hei 4-366808 and Hei 4-366809, a method is disclosed in which two layers liquid crystal system using a layer of chiral nematic liquid crystal as phase difference film is adopted. However, either methods described above are insufficient in improvement of the viewing angle and also had such problems that production cost is high and liquid crystal panels become heavy.

As a new method to solve the problems, In-Plane Switching (IPS) driving has recently come to attract public attention (R. Kiefer et al., JAPAN DISPLAY '92, 547 (1992); G. Baur, Freiburger Arbeitstagung Flussigkristalle, Abstract No. 22 (1993)). As characteristics in the structure of liquid crystal panels of the IPS drive, the fact that whereas an electrode is disposed on both upper and lower substrates, respectively, in conventional liquid crystal panels, a comb-shape electrode is disposed on the substrate only at one side in the IPS drive, and the fact that the direction of major axis of liquid crystal molecules is all the time in parallel to the substrates in the IPS drive can be mentioned. As advantages of the IPS drive,

{circle around (1)} cell thickness can be reduced since the electrode exists on the substrate only at one side,

{circle around (2)} By reduction of production cost can be expected since cell thickness can be reduced, and

{circle around (3)} By distance between electrodes is maintained constant, can be mentioned in addition to the fact that the viewing angle is expanded.

In order to actualize high speed response and low voltage drive in the IPS drive, the liquid crystalline compounds to be used are required to have a low viscosity and a high negative dielectric anisotropy. Also, as another example of attempts to improve the narrow viewing angle, a method which utilizes a vertical orientation of liquid crystal molecules and is disclosed in Laid-open Japanese Patent Publication No. Hei 2-176625 can be mentioned. One of the characteristics of this method is the use of liquid crystal compositions having a negative dielectric anisotropy. Meantime, as a conventional compound having a high negative dielectric anisotropy, the following compounds are disclosed in the patent publication shown below:

in the structural formula described above, R represents an alkyl group.

Compounds (e) (Japanese Patent Publication No. Sho 61-26899) are reported to have 2,3-dicyano—1,4-phenylene group in their partial structure and exhibit a high negative anisotropy. However, since they have cyano groups, their dependency of voltage holding ratio on temperature is large and viscosity is remarkably high, and thus the compounds can not be used as liquid crystal material for IPS drive utilizing TFT display mode. As described above, compounds having characteristics which are necessary for actualizing the high speed response and low voltage driving in the IPS driving, in a well balanced condition with each other, have not yet been known.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide liquid crystalline compounds which have such a high resistivity and high voltage holding ratio as can be used even for TFT display mode, are stable against heat and UV irradiation, have an effect as viscosity reducing agent, that is,

1) effect of raising clearing point of liquid crystal compositions,

2) effect of reducing viscosity of the compositions, and

3) effect of preventing the dielectric anisotropy of the compositions from lowering (or preventing the threshold voltage of the compositions from raising),

in a comprehensively well balanced condition, and further have a low viscosity and high negative dielectric anisotropy which can cope with the IPS driving or with such display devices of vertically oriented mode as described in Laid-open Japanese Patent Publication No. Hei 2-176625; to provide liquid crystal compositions comprising the liquid crystalline compound; and to provide liquid crystal display devices fabricated by using the liquid crystal composition.

Heretofore, as for the compounds which have a partial structure in which two phenylene groups are cross-linked with bonding group —CF₂O— and have an alkyl group as both terminal groups of the molecule, structural formula is disclosed in Laid-open Japanese Patent Publication No. Hei 2-289529 only with reference to two rings compound (f). It is true that structural formula is described in the patent publication mentioned above.

However, physical data of the compound and specific value of physical properties of the compound necessary for evaluating the utility as liquid crystalline compound are not disclosed at all, and thus the characteristics of the compound were not known in the least.

Then, specific two rings, three rings, or four rings compounds which have a partial structure in which two ring structures are cross-linked with bonding group —CF₂O— and have a group selected from an alkyl group, alkenyl group, alkoxy group, alkoxyalkyl group, and alkynyl group as both terminal groups of the molecule were devised and their physical properties were diligently investigated by the present inventors to find out that the compounds have not only a high clearing point but also an extremely low viscosity lower than expected at first, that the compounds exhibit a medium extent of dielectric anisotropy value (Δε=˜4.0), and further that the compounds having a partial structure of 2,3-difluoro-1,4-phenylene group and a bonding group of —COO—, —CF₂O—, or —OCF₂— at the same time not only exhibit a large negative dielectric anisotropy value but also are excellent in miscibility with other liquid crystal compounds, have a high resistivity and high voltage holding ratio, and are stable physically and chemically, leading to the accomplishment of the present invention.

Thus, the present invention is summarized as shown in the following paragraphs [1] to [29]:

[1] A liquid crystalline compound expressed by the general formula (1)

wherein R¹ and Y¹ represent an alkyl group having 1 to 20 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom, sulfur atom, or vinylene group, and one or more hydrogen atoms in the alkyl group may be replaced by fluorine atom or chlorine atom;

X¹, X², and X³ independently represent single bond, 1,2-ethylene group, vinylene group, —COO—, —CF₂O—, or —OCF₂— provided that at least one of X¹, X², and X³ represents —COO—, —CF₂O—, or —OCF₂—;

ring A¹, ring A², ring A³, and ring A⁴ independently represent trans-1,4-cyclohexylene group CH₂ group on which ring may be replaced by oxygen atom, or 1,4-phenylene group one or more hydrogen atoms of which may be replaced by fluorine atom or chlorine atom; and m and n are 0 or 1

provided that when X¹, X², or X³ represents —COO—, then at least one of ring A², ring A³, and ring A⁴ represents 2,3-difluoro-1,4-phenylene group, and Y¹ represents an alkoxy group;

when m=n=0 and X¹ represents —COO—, then ring A¹ represents 1,4-phenylene group at least one hydrogen atom in which group is replaced by fluorine atom;

when m=1, n=0, X¹ represents single bond or 1,2-ethylene group, and X² represents —COO—, then ring A² represents 1,4-phenylene group at least one hydrogen atom in which group is replaced by fluorine atom;

when m=n=1, X² represents —COO—, and X¹ represents single bond or 1,2-ethylene group, then ring A² represents 1,4-phenylene group at least one hydrogen atom in which group is replaced by fluorine atom;

when m=n=1, X³ represents —COO—, and X¹ and X² independently represent single bond or 1,2-ethylene group, then ring A³ represents 1,4-phenylene group at least one hydrogen atom in which group is replaced by fluorine atom; and

when m=n=0 and X¹ represents —CF₂O— or —OCF₂—, then ring A¹ or ring A⁴ represents trans-1,4cyclohexylene group, or 1,4-phenylene group at least one hydrogen atom in which group is replaced by chlorine atom or fluorine atom;

when m+n=1, X² or X³ represents —CF₂O—, ring A² or ring A³ represents 1,4-phenylene group, and A⁴ represents 1,4-phenylene group at least one hydrogen atom in which group may be replaced by a halogen atom, then Y¹ represents an alkyl or alkoxy group, and

each element which constitutes this compound may be replaced by its isotope.

[2] The liquid crystalline compound recited in paragraph [1] above wherein m=n=0, X¹ is —CF₂O—, and ring A¹ or ring A⁴ is 1,4-phenylene group at least one hydrogen atom in which group is replaced by fluorine atom or chlorine atom in the general formula (1).

[3] The liquid crystalline compound recited in paragraph [1] above wherein m=1, n=0, and X² is —COO— in the general formula (1).

[4] The liquid crystalline compound recited in [1] above wherein m=n=1 and X² is —COO— in the general formula (1).

[5] The liquid crystalline compound recited in paragraph [1] above wherein m=n=1 and X³ is —COO— in the general formula (1).

[6] The liquid crystalline compound recited in paragraph [3] above wherein ring A¹ is trans-1,4-cyclohexylene group and ring A² is 1,4-phenylene group in the general formula (1).

[7] The liquid crystalline compound recited in paragraph [3] above wherein both ring A¹ and ring A² are trans-1,4-cyclohexylene group in the general formula (1).

[8] The liquid crystalline compound recited in paragraph [6] above wherein X¹ is 1,2-ethylene group, X² is —COO—, and ring A² is 3-fluoro-1,4-phenylene group in the general formula (1).

[9] The liquid crystalline compound recited in paragraph [6] above wherein X¹ is vinylene group and X² is —COO— in the general formula (1).

[10] The liquid crystalline compound recited in paragraph [7] wherein X¹ is vinylene group and X² is —COO— in the general formula (1).

[11] The liquid crystalline compound recited in paragraph [1] above wherein m=1, n=0, and X¹ or X² is —CF₂O— or —OCF₂— in the general formula (1).

[12] The liquid crystalline compound recited in paragraph [1] above wherein both R¹ and Y¹ are an alkyl group in the general formula (1).

[13] The liquid crystalline compound recited in paragraph [11] above wherein at least one of R¹ and Y¹ is an alkenyl group in the general formula (1).

[14] The liquid crystalline compound recited in paragraph [11] above wherein X¹ is single bond, X² is —CF₂O— or —OCF₂—, both ring A¹ and ring A² are 1,4-cyclohexylene group, and ring A⁴ is 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom or chlorine atom in the general formula (1).

[15] The liquid crystalline compound recited in paragraph [1] above wherein m=n=1, and X¹, X², or X³ is —CF₂O— or OCF₂— in the general formula (1).

[16] The liquid crystalline compound recited in paragraph [15] above wherein R¹ and Y¹ are an alkyl group, both ring A¹ and ring A⁴ are 1,4-cyclohexylene group, both ring A² and ring A³ are 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom or chlorine atom, X² is —CF₂O— or —OCF₂—, and both X¹ and X³ are single bond in the general formula (1).

[17] The liquid crystalline compound recited in paragraph [15] above wherein R¹ and Y¹ are an alkyl group, both ring A¹ and ring A⁴ are 1,4-cyclohexylene group, both ring A² and ring A³ are 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom or chlorine atom, X² is —CF₂O— or —OCF₂—, and any one of X¹ and X³ is single bond and the other is 1,2-ethylene group in the general formula (1).

[18] The liquid crystalline compound recited in paragraph [15] above wherein at least one of R¹ and Y¹ is an alkenyl group in the general formula (1).

[19] A liquid crystal composition comprising at least two components and comprising at least one liquid crystalline compound expressed by the general formula (1).

[20] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom;

Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂OCF₂CF₂H, or —OCF₂CFHCF₃;

L¹ and L² independently represent hydrogen atom or fluorine atom;

Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OC₂—, or single bond;

ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom;

ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom; and

each atom which constitutes these compounds may be replaced by its isotope.

[21] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom;

Y³ represents CN group or —C≡C—CN;

ring D represents trans-1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group;

ring E represents trans-1,4-cyclohexylene, 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom, or pyrimidine-2,5-diyl group;

ring F represents trans-1,4-cyclohexylene or 1,4-phenylene group;

Z³ represents 1,2-ethylene group, —COO—, or single bond;

L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom;

a, b, and c are independently 0 or 1; and

each atom which constitutes these compounds may be replaced by its isotope.

[22] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, and comprising, as a second compound, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom;

ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom;

Z⁴ and Z⁵ independently represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH—, or single bond; and

each atom which constitutes these compounds may be replaced by its isotope.

[23] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom;

ring K represents trans-1,4-cyclohexylene or 1,4-phenylene group;

Z⁶ and Zindependently represent —CH₂CH₂-—, —CH₂O—, or single bond; and

each atom which constitutes these compounds may be replaced by its isotope.

[24] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12).

[25] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9).

[26] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6), and comprising, as a third component, at least one compounds selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9).

[27] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [18] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6), and comprising, as a fourth component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9).

[28] A liquid crystal composition comprising one or more optically active compounds in addition to the liquid crystal composition recited in any one of paragraphs [19] to [27] above.

[29] A liquid crystal display device using therein the liquid crystal composition recited in any one of paragraphs [19] to [28] above.

Any compounds of the present invention have a high clearing point and are low in viscosity. Among them, the compounds in which 2,3-difluoro-1,4-phenylene group is not selected as ring structure exhibit a medium extent of dielectric anisotropy value (Δε=˜4.0). On the other hand, the compounds in which 2,3-difluoro-1,4-phenylene group is selected as ring structure exhibit a large negative dielectric anisotropy value. Any type of these compounds are excellent in miscibility with other liquid crystal compounds, have a high resistivity and high voltage holding ratio, and are stable physically and chemically.

More specifically, the compounds in which an alkyl group is selected as terminal substituents of the molecule exhibit an extremely high voltage holding ratio and are very effective as viscosity reducing agent for display devices of TFT mode. The compounds in which an alkenyl group or another one is selected as terminal group of the molecule exhibit a comparatively large elastic constant ratio and are very useful as viscosity reducing agent for display devices of STN mode.

Since the compounds in which 2,3-difluoro-1,4-phenylene group is not selected as ring structure have a medium extent of dielectric anisotropy value compared with the compounds (c) or (d) described in the section of BACKGROUND ART, when the compounds are added to liquid crystal compositions having a high dielectric anisotropy and used for low voltage, it is possible to raise clearing point and further to maintain or reducing viscosity while suppressing the lowering of dielectric anisotropy (raising of threshold voltage).

On the other hand, since the compounds in which 2,3-difluoro-1,4-phenylene group is selected as ring structure are low in viscosity as described above and exhibit a large negative dielectric anisotropy value, it is possible to provide liquid crystal compositions and liquid crystal display devices which can be driven at a low voltage and can respond at a high speed in display devices of the IPS driving or the devices of such vertically oriented mode as described in Laid-open Japanese Patent Publication No. Hei 2-176625 by using the compounds of the present invention.

As a matter of course, while any compounds of the present invention exhibit preferable physical properties, liquid crystal compositions which meet their own purposes can be produced by using compounds in which proper R¹, Y¹, rings A¹, A², A³, and A⁴, X¹, X², X³, m, and n in the general formula (1) are selected.

That is, when the compounds are used for liquid crystal compositions of which temperature range of liquid crystal phase has to be at as high a temperature as possible, it is sufficient to use four rings compounds in which m=n=1, and when the circumstance is not so, it is sufficient to use two rings or three rings compounds.

When a particularly high voltage holding ratio is necessary, for example, for liquid crystal compositions used in active matrix, it is sufficient to select an alkyl group or alkoxy group as side chains R¹ and Y¹. When a large elastic constant ratio is necessary, for example, for STN liquid crystal compositions, it is sufficient to select a substituent having such an unsaturated bonding group as an alkenyl group and alkynyl group as side chains R¹ and Y¹.

In order to obtain compounds having a positive comparatively large dielectric anisotropy value, it is sufficient to select compounds having a partial structure in which two 1,4-phenylene groups are cross-linked with —CF₂O—, and substitute one or two fluorine atoms at the ortho position of phenyl ring at the side of difluoromethylene. In order to answer a still larger dielectric anisotropy value, it is sufficient to additionally substitute one or two fluorine atoms at the meta position on the phenyl ring at the side of oxygen atom in the fluorine atom substituted partial structure described above, and the purpose can be achieved by introducing fluorine atom so that the dipoles face the same direction.

In order to obtain compounds having a large negative dielectric anisotropy value, it is sufficient to select —CF₂O— or —COO— for one of bonding groups, X¹, X², and X³. Further, the compounds in which 2,3-difluoro-4-alkoxyphenyl group is selected instead of 2,3-difluoro-1,4-phenylene group exhibit a higher negative dielectric anisotropy.

Optical anisotropy value can also be optionally adjusted by selecting proper R¹, Y¹, rings A¹, A², A³, and A⁴, X¹, X², X³, m and n. That is, when a large optical anisotropy value is necessary, it is sufficient to select compounds having many 1,4-phenylene rings and having single bond as bonding group. When a small optical anisotropy value is necessary, it is sufficient to select compounds having many trans-1,4-cyclohexylene groups.

For the purpose of the present invention, the term “alkyl group” means a straight chain or branched alkyl group having 1 to 15 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable particularly from the viewpoint of low viscosity. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, isopropyl group, isobutyl group, isoamyl group, isohexyl group, 2-methylbutyl group, 2-methylpentyl group, and 3-methylpentyl group are preferable, and racemic modifications, S isomers, and R isomers are comprehended.

For the purpose of the present invention, the term “alkenyl group” means a straight chain alkenyl group having 2 to 15 carbon atoms. The alkenyl group preferably includes 1E-alkenyl, 2Z-alkenyl, 3E-alkenyl, and 4-alkenyl, and more specifically, 1-ethenyl, 1E-propenyl, 1E-butenyl, 1E-hexenyl, 2-propenyl, 2Z-butenyl, 2Z-pentenyl, 2Z-hexenyl, 3-butenyl, 3E-pentenyl, and 3E-hexenyl can be mentioned.

As rings A¹, A², A³, and A⁴, while benzene ring, cyclohexane ring, pyrimidine ring, pyridine ring, pyrazine ring, pyridazine ring, dioxane ring, dithian ring, and their halogen substituted ring can be mentioned, cyclohexane ring, benzene ring, and their halogen substituted ring are especially preferable.

Preferable embodiments of the compounds of the present invention expressed by the general formula (1) are compounds expressed by one of the following general formulas (1-1) to (1-217):

wherein R¹ and Y¹ have the same meaning as described above.

Any compounds expressed by one of the general formulas (1-1) to (1-11), (1-21) to (1-64), and (1-81) to (1-181) are low in viscosity and exhibit a medium extent of dielectric anisotropy. Among them, two rings or three rings compounds expressed by one of the general formulas (1-1) to (1-11) and (1-21) to (1-42) can remarkably lower only viscosity of liquid crystal compositions without lowering clearing point when added to the compositions as their component since the compounds are particularly low in viscosity and excellent in miscibility at low temperatures. Four rings compounds expressed by one of the general formulas (1-43) to (1-64) and (1-81) to (1-181) can raise only clearing point without raising viscosity when added to liquid crystal compositions as their component since the compounds have a wide temperature range of nematic phase and are low in viscosity.

Compounds expressed by one of the general formulas (1-97) to (1-136) and (1-160) to (1-181) have a characteristic that their optical anisotropy is high, in addition to the characteristic of the four rings compounds described above. Among them, tolan derivatives expressed by one of the general formulas (1-160) to (1-181) are low in viscosity and have an extremely high optical anisotropy, and thus they exhibit excellent characteristics as liquid crystal materials for STN.

Any compounds expressed by one of the general formulas (1-12) to (1-20), (1-65) to (1-70), and (1-182) to (1-217) can increase only dielectric anisotropy in negative numeral without raising viscosity of liquid crystal compositions when added to the compositions as their component since the compounds are extremely low in viscosity and exhibit such a characteristics that they have a high negative dielectric anisotropy, and thus the compounds can provide liquid crystal compositions which achieve both low voltage driving and high speed response in the display devices of IPS driving or such a vertical orientation mode as disclosed in Laid-open Japanese Patent Publication No. Hei 2-176625.

Further, any derivatives expressed by one of the general formulas (1-1) to (1-217) wherein one or more of R¹ and Y¹ are an alkenyl group exhibit an extremely large elastic constant ratio K33/K11. The derivatives are low in viscosity and exhibit a high clearing point compared with saturated compounds having the same skeleton. As described above, the compounds of the present invention have excellent characteristics, and thus liquid crystal compositions and liquid crystal display devices having improved characteristics can be provided by using the compounds.

Liquid crystal compositions of the present invention are described in more detail below. Liquid crystal compositions of the present invention preferably comprise at least one compound expressed by the general formula (1) in the ratio of 0.1 to 99.9% by weight to develop excellent characteristics.

More specifically, liquid crystal compositions provided according to the present invention are accomplished by mixing a compound optionally selected from the group of compounds expressed by one of the general formulas (2) to (4) depending on the purposes of liquid crystal compositions in addition to a first component comprising at least one compound expressed by the general formula (1).

As the compound expressed by one of the general formulas (2) to (4), the following compounds can preferably be mentioned:

wherein R² and Y² have the same meaning as described above.

Compounds expressed by one of the general formulas (2) to (4) have a positive dielectric anisotropy value and are remarkably excellent in thermal stability and chemical stability, and thus the compounds are particularly useful when liquid crystal compositions for TFT display mode, of which a high reliability represented by a high voltage holding ratio and a large resistivity is required, are produced.

When liquid crystal compositions for TFT display mode are produced, while a compound expressed by one of the general formulas (2) to (4) can optionally be used in the range of 0.1 to 99.9% by weight based on the total amount of liquid crystal composition in addition to a first component comprising at least one compound expressed by the general formula (1), the amount of the compound of the general formula (2) to (4) is preferably 10 to 97% by weight and more desirably 40 to 95% by weight.

Also, when liquid crystal compositions for STN display mode or TN display mode are produced, a compound expressed by one of the general formulas (2) to (4) can be used in addition to the first component comprising at least one compound expressed by the general formula (1), but the amount of the compound of the general formula (2) to (4) is preferably less than 50% by weight in this case.

To the liquid crystal compositions thus obtained comprising a compound expressed by the general formula (1) and a compound expressed by one of the general formulas (2) to (4), the compound selected from a group of the compounds expressed by one of the general formulas (5) to (12) may further be added for the. purpose of adjusting viscosity of the liquid crystal compositions.

As the compound expressed by the general formula (5) or (6), the following compounds can preferably be mentioned:

wherein R³, R⁴, and Y³ have the same meaning as described above.

Compounds expressed by the general formula (5) or (6) have a large positive dielectric anisotropy value and thus are used particularly for the purpose of lowering threshold voltage of liquid crystal compositions. They are used also for the purpose of adjusting optical anisotropy value and widening the temperature range of nematic phase such as raising clearing point. Further, the compounds are used for the purpose of improving the steepness of voltage-transmittance curve of liquid crystal compositions for STN display mode or TN display mode.

When the amount of the compound expressed by the general formula (5) or (6) is increased, threshold voltage of liquid crystal compositions lowers and viscosity increases. Accordingly, it is advantageous to use the compound in a large quantity so far as the viscosity of liquid crystal compositions satisfies required characteristics, since the compositions can be driven at a low voltage. While the compound expressed by the general formula (5) or (6) can be used in any amount in the range of 0.1 to 99.9% by weight when liquid crystal compositions for STN display mode or TN display mode are produced, the amount is preferably 10 to 97% by weight and more desirably 40 to 95% by weight.

As the compound used in the present invention and expressed by one of the general formula (7) to (9), the following compounds can preferably be mentioned:

wherein R⁵ and R⁶ have the same meaning as described above.

Compounds expressed by one of the general formulas (7) to (9) are small in absolute value of dielectric anisotropy and are close to neutral. Compounds expressed by the general formula (7) are used principally for the purpose of adjusting viscosity and adjusting optical anisotropy value of liquid crystal compositions. Compounds expressed by the general formula (8) or (9) are used for the purpose of widening the temperature range of nematic phase such as raising clearing point of liquid crystal compositions or for the purpose of adjusting the optical anisotropy value.

When the amount of the compound expressed by one of the general formulas (7) to (9) to be used is increased, threshold voltage of liquid crystal compositions rises and their viscosity lowers. Accordingly, it is desirable to use a large quantity of the compound so far as the threshold voltage of liquid crystal compositions is satisfied. Amount of the compound expressed by 0 one of the general formulas (7) to (9) to be used is 40% by weight or less and more desirably less than 35% by weight when liquid crystal compositions for TFT display mode are produced. Further, the amount is 70% by weight or less and more desirably less than 60% by weight when liquid crystal compositions for STN display mode or TN display mode are produced.

As the compounds used in the present invention and expressed by one of the general formulas (10) to (12), the following compounds can preferably be mentioned:

wherein R⁷ and R⁸ have the same meaning as described above.

Compounds expressed by one of the general formulas (10) to (12) have a negative dielectric anisotropy value. Accordingly, the compounds can control the elastic constant of liquid crystal compositions, which is a function of dielectric anisotropy value, by mixing with a compound having a positive dielectric anisotropy value, and thereby the steepness of voltage-transmittance curve of liquid crystal compositions can be controlled. Accordingly, the compounds can be used for various driving modes.

Compounds expressed by one of the general formulas (10) to (12) can optionally be used in the range of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, and more desirably 10 to 60% by weight when liquid crystal compositions for TFT display mode, STN display mode, or TN display mode are produced.

Except such specific cases as liquid crystal compositions for OCB (Optically Compensated Birefringence) mode, an optically active compound is sometimes added to liquid crystal compositions generally for the purpose of inducing helical structure of liquid crystals to adjust required twisting angle and to prevent the reverse twist, and the optically active compound can be added in the same way even in the liquid crystal compositions of the present invention. While any known optically active compounds can be used for such purposes, preferable optically active compounds can be mentioned as follows:

Usually, one of these optically active compounds is added to the liquid crystal compositions of the present invention to adjust the pitch of the twist of liquid crystals. The twist pitch is preferably adjusted in the range of 10 to 200 pm in the case of liquid crystal compositions for TFT display mode or TN display mode. In the case of liquid crystal compositions for STN display mode, the pitch is preferably adjusted in the range of 6 to 20 μm. In the case of bistable TN mode, the pitch is preferably adjusted in the range of 1.5 to 4 μm. Further, two or more kind of optically active compounds may be added for the purpose of adjusting the dependency of the pitch on temperature.

Liquid crystal compositions of the present invention can be produced by methods which are known in public by themselves. Generally, a method wherein various components are dissolved in each other at a high temperature is adopted.

Liquid crystal compositions of the present invention can be used as ones for guest-host (GH) mode by adding a dichroic dye such as merocyanine type, styryl type, azo type, azomethine type, azoxy type, quinophthalone type, anthraquinone type, or tetrazine type dye. Liquid crystal compositions of the present invention can also be used as ones for NCAP which is prepared by the microencapsulation of a nematic liquid crystal, or for a polymer dispersed liquid crystal display device (PDLCD) represented by polymer network liquid crystal display device (PNLCD) prepared by forming polymers of three-dimensional reticulated structure in a liquid crystal. In addition, the liquid crystal compositions of the present invention can be used as ones for electrically controlled birefringence (ECB) mode or dynamic scattering (DS) mode.

As nematic liquid crystal compositions comprising the liquid crystalline compound of the present invention, the following composition examples can be mentioned. In the composition examples, compounds are designated by using symbols according to the definitions shown in Table 1 below.

Further, in the case where hydrogen atoms of trans-1,4-cyclohexylene are replaced by deuterium atom at positions Q¹, Q², and Q³, it is designated as symbol H [1D, 2D, 3D]. In the case where the hydrogen atom is replaced at positions Q⁵, Q⁶, and Q⁷, it is designated as symbol H [5D, 6D, 7D]. Thus, the position where deuterium atom substituted is indicated by the number in the parenthesis.

TABLE 1 Method for designating compounds by using symbols R—(A₁)—Z₁— . . . —Z_(n)—(A_(n))—X 1) Left side terminal group R— Symbol C_(n)H_(2n+1)— n— C_(n)H_(2n+1)O— nO— C_(n)H_(2n+1)OC_(m)H_(2m)— nOm— CH₂═CH— V— CH₂═CHC_(n)H_(2n)— Vn— C_(n)H_(2n+1)CH═CHC_(m)H_(2m)— nVm— C_(n)H_(2n+1)CH═CHC_(m)H_(2m)CH═CHC_(k)H_(2k)— nVmVk— 2) Ring structure —(A₁)—, —(A_(n))— Symbol

B

B(F)

B(2F,3F)

B(F,F)

H

Py

D

Ch 3) Bonding group —Z₁—, —Z_(n)— Symbol —C₂H₄— 2 —C₄H₈— 4 —COO— E —C≡C— T —CH═CH— V —CF₂O— CF2O —OCF₂— OCF2 4) Right side terminal group —X Symbol —F —F —Cl —CL —CN —C —CF₃ —CF3 —OCF₃ —OCF3 —OCF₂H —OCF2H —C_(n)H_(2n+1) —n —OC_(n)H_(2n+1) —On —COOCH₃ —EMe —C_(n)H_(2n)CH═CH₂ —nV —C_(m)H_(2m)CH═CHC_(n)H_(2n+1) —mVn —C_(m)H_(2m)CH═CHC_(n)H_(2n)F —mVnF —CH═CF₂ —VFF —C_(n)H_(2n)CH═CF₂ —nVFF —C≡C—CN —TC 5) Example of designation Example 1  3-H2B(F,F)B(F)—F

Example 2  3-HB(F)TB-2

Example 3  1V2—BEB(F,F)—C

COMPOSITION EXAMPLE 1

3-H2B(F)EB(2F,3F)—O2 15.0% 1V2-BEB(F,F)—C 5.0% 3-HB—C 25.0% 2-BTB-1 11.0% 3-HH-4 10.0% 3-HHB-1 10.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0% CM33 0.8 part

COMPOSITION EXAMPLE 2

5-HVHEB(2F,3F)—O2 7.0% V2-HB—C 12.0% 1V2-HB—C 12.0% 3-HB—C 15.0% 3-H [1D,2D,3D]—C 9.0% 3-HB(F)—C 5.0% 2-BTB-1 2.0% 3-HH-4 6.0% 3-HH—VFF 6.0% 2-H [1D,2D,3D] HB—C 3.0% 3-HHB—C 3.0% 3-HB(F)TB-2 6.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4.0%

COMPOSITION EXAMPLE 3

3-H2B(F)EB(2F,3F)—O2 10.0% 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 15.0% 4O1-BEB(F)—C 13.0% 5O1-BEB(F)—C 11.0% 2-HHB(F)—C 15.0% 3-HHB(F)—C 15.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB—O1 4.0%

COMPOSITION EXAMPLE 4

3-H2B(F)EB(2F,3F)—O2 6.0% 5-HVHEB(2F,3F)—O2 6.0% 5-PyB—F 4.0% 3-PyB(F)—F 4.0% 2-BB—C 5.0% 4-BB—C 4.0% 5-BB—C 5.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB—O5 3.0% 6-PyB—O6 3.0% 6-PyB—O7 3.0% 3-PyBB—F 6.0% 4-PyBB—F 6.0% 5-PyBB—F 6.0% 3-HHB-1 5.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0%

COMPOSITION EXAMPLE 5

5-HVHEB(2F,3F)—O2 7.0% 5-HBCF2OB(2F,3F)—O2 13.0% 3-HB—C 18.0% 7-HB—C 3.0% 1O1-HB—C 10.0% 3-HB(F)—C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 1O1-HH-3 4.0% 2-BTB—O1 5.0% 3-HHB—F 4.0% 3-HHB—O1 4.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0%

COMPOSITION EXAMPLE 6

3-H2B(F)EB(2F,3F)—O2 4.0% 5-HVHEB(2F,3F)—O2 4.0% 5-HBCF2OB(2F,3F)—O2 4.0% 5-BEB(F)—C 5.0% V—HB—C 11.0% 5-PyB—C 6.0% 4-BB-3 11.0% 3-HH-2V 6.0% 5-HH—V 11.0% V—HHB-1 7.0% V2-HHB-1 11.0% 3-HHB-1 5.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0%

COMPOSITION EXAMPLE 7

3-H2B(F)EB(2F,3F)—O2 7.0% 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 12.0% 5O1-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 16.0% 3-HB—O2 10.0% 3-HH-4 3.0% 3-HHB—F 3.0% 3-HHB-1 3.0% 3-HHB—O1 2.0% 3-HBEB—F 4.0% 3-HHEB—F 7.0% 5-HHEB—F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 5.0%

COMPOSITION EXAMPLE 8

5-HBCF2OB(2F,3F)—O2 10.0% 2-BEB—C 12.0% 3-BEB—C 4.0% 4-BEB—C 6.0% 3-HB—C 28.0% 3-HEB—O4 12.0% 4-HEB—O2 8.0% 5-HEB—O1 8.0% 3-HEB—O2 6.0% 3-HHB-1 2.0% 3-HHB—O1 4.0%

COMPOSITION EXAMPLE 9

3-H2B(F)EB(2F,3F)—O2 5.0% 5-HVHEB(2F,3F)—O2 5.0% 5-HBCF2OB(2F,3F)—O2 5.0% 2-BEB—C 10.0% 5-BB—C 12.0% 7-BB—C 7.0% 1-BTB-3 7.0% 2-BTB-1 10.0% 1O—BEB-2 10.0% 1O—BEB-5 10.0% 2-HHB-1 4.0% 3-HHB—F 4.0% 3-HHB-1 7.0% 3-HHB—O1 4.0%

COMPOSITION EXAMPLE 10

5-HVHEB(2F,3F)—O2 7.0% 5-HBCF2OB(2F,3F)—O2 8.0% 1V2-BEB(F,F)—C 8.0% 3-HB—C 10.0% V2V—HB—C 14.0% V2V—HH-3 16.0% 3-HB—O2 4.0% 3-HHB-1 10.0% 3-HHB-3 3.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%

COMPOSITION EXAMPLE 11

5-HVHEB(2F,3F)—O2 5.0% 5-HBCF2OB(2F,3F)—O2 6.0% 5-BTB(F)TB-3 10.0% V2-HB—TC 10.0% 3-HB—TC 10.0% 3-HB—C 10.0% 5-HB—C 7.0% 5-BB—C 3.0% 2-BTB-1 10.0% 2-BTB—O1 5.0% 3-HH-4 5.0% 3-HHB-1 10.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB(F)TB-2 3.0%

COMPOSITION EXAMPLE 12

5-HVHEB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 4.0% 1V2-BEB(F,F)—C 6.0% 3-HB—C 18.0% 2-BTB-1 10.0% 5-HH—VFF 30.0% 1-BHH—VFF 8.0% 1-BHH-2VFF 4.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0%

COMPOSITION EXAMPLE 13

3-H2B(F)EB(2F,3F)—O2 5.0% 5-HVHEB(2F,3F)—O2 10.0% 5-HBCF2OB(2F,3F)—O2 10.0% 2-HB—C 5.0% 3-HB—C 12.0% 3-HB—O2 12.0% 2-BTB-1 3.0% 3-HHB-1 3.0% 3-HHB—F 4.0% 3-HHB—O1 2.0% 3-HHEB—F 4.0% 5-HHEB—F 4.0% 2-HHB(F)—F 7.0% 3-HHB(F)—F 7.0% 5-HHB(F)—F 7.0% 3-HHB(F,F)—F 5.0%

COMPOSITION EXAMPLE 14

5-HBCF2OB(2F,3F)—O2 10.0% 2-HHB(F)—F 17.0% 3-HHB(F)—F 17.0% 5-HHB(F)—F 16.0% 2-H2HB(F)—F 10.0% 3-H2HB(F)—F 5.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 13.0% CN 0.3 part

COMPOSITION EXAMPLE 15

5-HVHEB(2F,3F)—O2 8.0% 5-HBCF2OB(2F,3F)—O2 5.0% 7-HB(F)—F 5.0% 5-H2B(F)—F 5.0% 3-HB—O2 10.0% 3-HH-4 2.0% 3-HH [5D,6D,7D]-4 3.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 5.0% 5-HH [5D,6D,7D] B(F)—F 10.0% 3-H2HB(F)—F 5.0% 2-HBB(F)—F 3.0% 3-HBB(F)—F 3.0% 5-HBB(F)—F 6.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 6.0% 3-HHB—O1 5.0% 3-HHB-3 4.0%

COMPOSITION EXAMPLE 16

3-H2B(F)EB(2F,3F)—O2 3.0% 5-HVHEB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 4.0% 7-HB(F,F)—F 3.0% 3-HB—O2 7.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 2-HBB(F)—F 9.0% 3-HBB(F)—F 9.0% 5-HBB(F)—F 16.0% 2-HBB—F 4.0% 3-HBB—F 4.0% 5-HBB—F 3.0% 3-HBB(F,F)—F 5.0% 5-HBB(F,F)—F 10.0%

COMPOSITION EXAMPLE 17

5-HBCF2OB(2F,3F)—O2 15.0% 7-HB(F,F)—F 3.0% 3-H2HB(F,F)—F 12.0% 4-H2HB(F,F)—F 10.0% 5-H2HB(F,F)—F 10.0% 3-HHB(F,F)—F 5.0% 4-HHB(F,F)—F 5.0% 3-HH2B(F,F)—F 15.0% 3-HBB(F,F)—F 12.0% 5-HBB(F,F)—F 7.0% 3-HBCF2OB(F,F)—F 6.0%

COMPOSITION EXAMPLE 18

3-H2B(F)EB(2F,3F)—O2 10.0% 7-HB(F,F)—F 5.0% 3-H2HB(F,F)—F 12.0% 3-HHB(F,F)—F 10.0% 4-HHB(F,F)—F 5.0% 3-HBB(F,F)—F 10.0% 3-HHEB(F,F)—F 10.0% 4-HHEB(F,F)—F 3.0% 5-HHEB(F,F)—F 3.0% 2-HBEB(F,F) 3.0% 3-HBEB(F,F) 5.0% 5-HBEB(F,F) 3.0% 3-HDB(F,F) 15.0% 3-HHBB(F,F)—F 6.0%

COMPOSITION EXAMPLE 19

5-HBCF2OB(2F,3F)—O2 10.0% 3-BCF2OB(2F,3F)—O2 10.0% 3-HHB(F,F)—F 9.0% 3-H2HB(F,F)—F 8.0% 4-H2HB(F,F)—F 8.0% 5-H2HB(F,F)—F 8.0% 3-HBB(F,F)—F 11.0% 5-HBB(F,F)—F 10.0% 3-H2BB(F,F)—F 10.0% 5-HHBB(F,F)—F 3.0% 5-HHEBB—F 2.0% 3-HH2BB(F,F)—F 3.0% 1O1-HBBH-4 4.0% 1O1-HBBH-5 4.0%

COMPOSITION EXAMPLE 20

5-HBCF2OB(2F,3F)—O2 4.0% 5-B2BCF2OB(2F,3F)—O2 4.0% 3-BCF2OB(2F,3F)—O2 4.0% 5-HB—F 12.0% 6-HB—F 9.0% 7-HB—F 7.0% 2-HHB—OCF3 7.0% 3-HHB—OCF3 7.0% 4-HHB—OCF3 7.0% 5-HHB—OCF3 5.0% 3-HH2B—OCF3 4.0% 5-HH2B—OCF3 4.0% 3-HHB(F,F)—OCF3 5.0% 3-HBB(F)—F 8.0% 3-HH2B(F)—F 3.0% 3-HB(F)BH-3 3.0% 5-HBBH-3 3.0% 3-HHB(F,F)—OCF2H 4.0%

COMPOSITION EXAMPLE 21

3-H2B(F)EB(2F,3F)—O2 15.0% 3-HEB—O4 23.0% 4-HEB—O2 18.0% 5-HEB—O1 18.0% 3-HEB—O2 14.0% 5-HEB—O2 12.0%

COMPOSITION EXAMPLE 22

5-HBCF2OB(2F,3F)—O2 15.0% 5-HVHEB(2F,3F)—O2 5.0% 3-HB—O2 10.0% 3-HB—O4 10.0% 3-HEB—O4 16.0% 4-HEB—O2 13.0% 5-HEB—O1 13.0% 3-HEB—O2 10.0% 5-HEB—O2 8.0%

COMPOSITION EXAMPLE 23

5-HBCF2OB(2F,3F)—O2 15.0% 3-HB—O2 15.0% 3-HB—O4 10.0% 3-HEB—O4 10.0% 4-HEB—O2 7.0% 5-HEB—O1 7.0% 3-HEB—O2 6.0% 5-HEB—O2 5.0% 3-HB(2F,3F)—O2 7.0% 5-HHB(2F,3F)—O2 5.0% 5-HBB(2F,3F)-2 5.0% 5-HBB(2F,3F)—O2 4.0% 5-BB(2F,3F)B-3 4.0%

COMPOSITION EXAMPLE 24

3-BCF2OB(2F,3F)—O2 20.0% 3-H2B(F)EB(2F,3F)—O2 15.0% 5-HBCF2OB(2F,3F)—O2 15.0% 3-HB(2F,3F)—O2 20.0% 5-HHB(2F,3F)—O2 10.0% 5-HHB(2F,3F)-1O1 5.0% 5-HBB(2F,3F)-2 10.0% 5-HBB(2F,3F)-1O1 5.0%

COMPOSITION EXAMPLE 25

3-BCF2OB(2F,3F)—O2 10.0% 3-H2B(F)EB(2F,3F)—O2 5.0% 5-HVHEB(2F,3F)—O2 5.0% 5-BBCF2OB(2F,3F)—O2 5.0% 3-DB—C 10.0% 4-DB—C 10.0% 2-BEB—C 12.0% 3-BEB—C 4.0% 3-PyB(F)—F 6.0% 3-HEB—O2 3.0% 5-HEB—O2 4.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 1O—BEB-2 4.0% 3-HHB-1 3.0% 3-HHEBB—C 3.0% 3-HBEBB—C 3.0% 5-HBEBB—C 3.0%

COMPOSITION EXAMPLE 26

3-H2HCF2OB(2F,3F)—O2 10.0% 3-HVBCF2OB(2F,3F)—O2 5.0% 5-H2BCF2OB(2F,3F)—O2 5.0% 3-HHBCF2OB(2F,3F)—O2 3.0% 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 12.0% 5O1-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 10.0% 3-HH—EMe 5.0% 3-HB—O2 18.0% 7-HEB—F 2.0% 3-HHEB—F 2.0% 5-HHEB—F 2.0% 3-HBEB—F 4.0% 2O1-HBEB(F)—C 2.0% 3-HB(F)EB(F)—C 2.0% 3-HBEB(F,F)—C 2.0% 3-HHB—F 2.0% 3-HHB-3 1.0% 3-HEBEB—F 2.0% 3-HEBEB-1 2.0%

COMPOSITION EXAMPLE 27

3-B(F)EB(2F,3F)—O2 5.0% 3-BCF2OB(2F,3F)—O2 5.0% 5-HBCF2OB(2F,3F)—O2 5.0% 5-H2BCF2OB(2F,3F)—O2 10.0% 5-B2BCF2OB(2F,3F)—O2 15.0% 5-HB—CL 4.0% 7-HB—CL 4.0% 1O1-HH-5 3.0% 2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0.% 4-HHB—CL 4.0% 5-HHB—CL 8.0% 3-H2HB(F)—CL 4.0% 3-HBB(F,F)—F 10.0% 5-H2BB(F,F)—F 9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0%

COMPOSITION EXAMPLE 28

3-B(F)EB(2F,3F)—O2 5.0% 5-HVBEB(2F,3F)—O3 5.0% 5-H2B(F)EB(2F,3F)—O2 5.0% 5-H4HB(F,F)—F 7.0% 5-H4HB—OCF3 15.0% 3-H4HB(F,F)—CF3 3.0% 3-HB—CL 6.0% 5-HB—CL 4.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 10.0% 5-HVHB(F,F)—F 5.0% 3-HHB—OCF3 5.0% 3-H2HB—OCF3 5.0%. V—HHB(F)—F 5.0% 3-HHB(F)—F 5.0% 5-HHEB—OCF3 2.0% 3-HBEB(F,F)—F 5.0% 5-HH—V2F 3.0%

COMPOSITION EXAMPLE 29

5-B(F)CF2OB(2F,3F)—O1 5.0% 3-H2HB(F)EB(2F,3F)—O2 3.0% 3-HH2BCF2OB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 5.0% 2-HHB(F)—F 2.0% 3-HHB(F)—F 2.0% 5-HHB(F)—F 2.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 10.0% 2-H2BB(F)—F 9.0% 3-H2BB(F)—F 9.0% 3-HBB(F,F)—F 15.0% 5-HBB(F,F)—F 19.0% 1O1-HBBH-4 4.0%

COMPOSITION EXAMPLE 30

5-B(F)CF2OB(2F,3F)—O1 5.0% 5-HBCF2OB(2F,3F)—O2 5.0% 5-HB—CL 12.0% 3-HH-4 2.0% 3-HB—O2 20.0% 3-H2HB(F,F)—F 5.0% 3-HHB(F,F)—F 8.0% 3-HBB(F,F)—F 6.0% 2-HHB(F)—F 5.0% 3-HHB(F)—F 5.0% 5-HHB(F)—F 5.0% 2-H2HB(F)—F 2.0% 3-H2HB(F)—F 1.0% 5-H2HB(F)—F 2.0% 3-HHBB(F,F)—F 4.0% 3-HBCF2OB—OCF3 4.0% 5-HBCF2OB(F,F)—OCF3 4.0% 3-HHB-1 3.0% 3-HHB—O1 2.0%

COMPOSITION EXAMPLE 31

5-HBCF2OB-3 8.0% 5-HBCF2OBH-3 7.0% 7-HB(F)—F 14.0% 2-HHB(F)—F 11.0% 3-HHB(F)—F 11.0% 5-HHB(F)—F 11.0% 2-H2HB(F)—F 5.3% 3-H2HB(F)—F 2.6% 5-H2HB(F)—F 5.3% 2-HBB(F)—F 6.2% 2-HBB(F)—F 6.2% 2-HBB(F)—F 12.4%

COMPOSITION EXAMPLE 32

5-HBCF2OBH-3 7.0% 3-H2BCF2OBH-3 7.0% 3-H2BCF2OBH-5 6.0% 7-HB(F,F)—F 4.0% 3-HHB(F,F)—F 6.0% 3-H2HB(F,F)—F 5.0% 3-HBB(F,F)—F 12.0% 5-HBB(F,F)—F 12.0% 3-H2BB(F,F)—F 5.0% 4-H2BB(F,F)—F 5.0% 5-H2BB(F,F)—F 5.0% 3-HBEB(F,F)—F 2.0% 4-HBEB(F,F)—F 2.0% 5-HBEB(F,F)—F 2.0% 3-HHEB(F,F)—F 12.0% 4-HHEB(F,F)—F 4.0% 5-HHEB(F,F)—F 4.0%

COMPOSITION EXAMPLE 33

3-HBCF2OB-3 5.0% 3-BCF2OBH-5 5.0% 3-H2HB(F,F)—F 9.0% 5-H2HB(F,F)—F 8.0% 3-HHB(F,F)—F 9.0% 4-HHB(F,F)—F 5.0% 3-HH2B(F,F)—F 11.0% 5-HH2B(F,F)—F 7.0% 3-HBB(F,F)—F 14.0% 5-HBB(F,F)—F 14.0% 3-HHEB(F,F)—F 9.0% 3-HHBB(F,F)—F 2.0% 3-HH2BB(F,F)—F 2.0%

COMPOSITION EXAMPLE 34

3-HBCF2OBH-3 6.0% 3-HBCF2OBH-5 4.0% 3-H2BCF2OBH-2 5.0% 7-HB(F,F)—F 4.0% 7-HB(F)—F 6.0% 2-HHB(F)—F 11.5% 3-HHB(F)—F 11.5% 5-HHB(F)—F 11.5% 2-H2HB(F)—F 3.0% 3-H2HB(F)—F 1.5% 5-H2HB(F)—F 3.0% 3-H2HB(F,F)—F 5.0% 4-H2HB(F,F)—F 4.0% 5-H2HB(F,F)—F 4.0% 3-HHB(F,F)—F 7.0% 3-HH2B(F,F)—F 7.0% 5-HH2B(F,F)—F 6.0%

COMPOSITION EXAMPLE 35

3-HB(F)CF2OB-3 8.0% 3-HB(F,F)CF2OB-5 5.0% 2-HBCF2OBH-2 7.0% 7-HB(F,F)—F 4.0% 2-HHB(F)—F 11.1% 3-HHB(F)—F 11.2% 5-HHB(F)—F 11.2% 2-H2HB(F)—F 3.0% 3-H2HB(F)—F 1.5% 5-H2HB(F)—F 3.0% 3-H2HB(F,F)—F 5.0% 4-H2HB(F,F)—F 3.0% 5-H2HB(F,F)—F 3.0% 3-HHB(F,F)—F 8.0% 4-HHB(F,F)—F 4.0% 3-HH2B(F,F)—F 6.0% 5-HH2B(F,F)—F 6.0%

COMPOSITION EXAMPLE 36

3-HBCF2OB-5 7.0% 3-HB(F)CF2OBH-3 5.0% 3-HB(F)CF2OBTB-3 3.0% 3-HB—Cl 7.0% 7-HB(F,F)—F 10.0% 2-HBB(F)—F 6.5% 3-HBB(F)—F 6.5% 5-HBB(F)—F 13.0% 2-HHB—CL 5.0% 4-HHB—CL 8.0% 5-HHB—CL 5.0% 3-HBB(F,F)—F 10.0% 5-HBB(F,F)—F 8.0% 3-HB(F)VB-2 3.0% 3-HB(F)VB-3 3.0%

COMPOSITION EXAMPLE 37

3-BCF2OBH—V 5.0% 5-HB(F,F)CF2OBH-3 3.0% 2-BTBCF2OBH-2 3.0% 3-BTB(F)CF2OBH-3 3.0% 5-HB—CL 5.0% 7-HB—CL 6.0% 2-HBB(F)—F 7.0% 3-HBB(F)—F 7.0% 5-HBB(F)—F 14.0% 2-HHB—CL 5.0% 4-HHB—CL 5.0% 5-HHB—CL 4.0% 3-HBB(F,F)—F 16.0% 5-HBB(F,F)—F 14.0% 3-HB(F)TB-2 3.0%

COMPOSITION EXAMPLE 38

5-HBCF2OBH-3 6.0% 3-HBCF2OBH-3 6.0% 5-HBCF2OBTB-3 3.0% 2-HHB(F)—F 8.0% 3-HHB(F)—F 8.0% 5-HHB(F)—F 8.0% 3-HHB(F,F)—F 6.0% 5-HHB(F,F)—F 5.0% 3-H2HB(F,F)—F 7.0% 4-H2HB(F,F)—F 7.0% 5-H2HB(F,F)—F 7.0% 3-HH2B(F,F)—F 12.0% 5-HH2B(F,F)—F 8.0% 2-HBB—F 3.0% 3-HBB—F 3.0% 3-HHB-1 3.0%

COMPOSITION EXAMPLE 39

5-HBCF2OB-3 5.0% 2-HB(F)CF2OB-3 5.0% 3-HB(F)CF2OB-3 5.0% 7-HB(F)—F 4.0% 2-HHB(F)—F 13.0% 3-HHB(F)—F 13.0% 5-HHB(F)—F 13.0% 2-H2HB(F)—F 6.0% 3-H2HB(F)—F 3.0% 5-H2HB(F)—F 6.0% 2-HBB(F)—F 3.0% 3-HBB(F)—F 3.0% 5-HBB(F)—F 6.0% 3-HBB—F 2.0% 3-HHB—F 3.0% 3-HB—O2 5.0% 3-HHB-1 3.0% 1O1-HBBH-3 2.0%

COMPOSITION EXAMPLE 40

5-HBCF2OB-3 8.0% 3-BCF2OBH—V 8.0% 2-BCF2OBH-2V 8.0% 3-HB(F)CF2OBH-3 6.0% 7-HB(F,F)—F 5.0% 5-H2B(F)—F 5.0% 2-HHB(F)—F 4.0% 3-HHB(F)—F 4.0% 5-HHB(F)—F 4.0% 2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0% 5-HBB(F)—F 16.0% 2-HBB—F 4.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0%

COMPOSITION EXAMPLE 41

3-HB(F,F)CF2OB-1 4.0% 3-HB(F,F)CF2OBH-3 4.0% 2-BTB(F,F)CF2OBH-2 2.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 2-HBB(F)—F 5.0% 3-HBB(F)—F 5.0% 5-HBB(F)—F 10.0% 3-HHB(F,F)—F 7.0% 5-HHB(F,F)—F 4.0% 3-HH2B(F,F)—F 8.0% 5-HH2B(F,F)—F 8.0% 5-H2HB(F,F)—F 5.0% 5-HHEBB—F 2.0% 3-HB—O2 4.0% 3-HHB—O1 2.0%

COMPOSITION EXAMPLE 42

5-HBCF2OB-3 5.0% 3-BCF2OBH—V 4.0% 5-HBCF2OBH-3 5.0% 3-H2BCF2OBH-3 5.0% 2-HHB(F)—F 4.0% 3-HHB(F)—F 4.0% 5-HHB(F)—F 4.0% 2-HBB(F)—F 4.0% 3-HBB(F)—F 4.0% 5-HBB(F)—F 8.0% 4-H2BB(F)—F 6.0% 5-H2BB(F)—F 6.0% 3-H2BB(F,F)—F 4.0% 4-H2BB(F,F)—F 5.0% 5-H2BB(F,F)—F 4.0% 3-HBB(F,F)—F 12.0% 5-HBB(F,F)—F 8.0% 3-HH2B(F,F)—F 4.0% 5-HH2B(F,F)—F 4.0%

COMPOSITION EXAMPLE 43

5-HBCF2OB-3 6.0% 3-BCF2OBH—V 4.0% 5-HBCF2OBH-3 5.0% 3O1-BEB(F)—C 12.0% V2-HB—C 10.0% 3-HB—O2 4.0% 2-BTB—O1 5.0% 3-BTB—O1 5.0% 4-BTB—O1 5.0% 4-BTB—O2 5.0% 5-BTB—O1 5.0% 3-HHB—O1 3.0% 3-H2BTB-2 2.0% 3-H2BTB-3 3.0% 3-H2BTB-4 3.0% 3-HB(F)TB-2 3.0% 3-HB(F)TB-3 3.0% 3-HB(F)TB-4 5.0% 2-PyBH-3 4.0% 2-PyBH-3 4.0% 3-PyBB-2 4.0%

COMPOSITION EXAMPLE 44

5-HBCF2OBH-3 6.0% 3-H2BCF2OBH-3 6.0% 3-H2BCF2OBH-5 5.0% V2-HB—C 9.0% 1V2-HB—C 9.0% 3-HB—C 14.0% 1O1-HB—C 8.0% 2O1-HB—C 4.0% 2-HHB—C 5.0% 3-HHB—C 5.0% 3-HH-4 8.0% 1O1-HH-5 5.0% 2-BTB—O1 8.0% 3-HHB-1 4.0% 3-HHB-3 4.0%

COMPOSITION EXAMPLE 45

3-BCF2OBH—V 3.0% 5-BCF2OBH-2V 4.0% 3-BCF2OBH-2V1 4.0% 3-H2BCF2OBH-5 4.0% 1V2-BEB(F,F)—C 12.0% 3O1-BEB(F)—C 12.0% 2-HB—C 12.0% 3-HB—C 19.0% 2-HHB—C 4.0% 3-HHB—C 5.0% 4-HHB—C 4.0% 5-HHB—C 4.0% 3-HB—O2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%

COMPOSITION EXAMPLE 46

5-HBCF2OB-3 10.0% 3-HB(F)CF2OB-3 10.0% 2-HB(F)CF2OBH—V 4.0% 3-HB(F)CF2OBH—V1 3.0% 3-BTBCF2OBH-3 3.0% V2-HB—C 12.0% 1V2-HB—C 11.0% 1V2-BEB(F,F)—C 11.0% 2-BTB-1 5.0% 4-BTB—O2 5.0% 5-BTB—O1 5.0% 3-HH—EMe 4.0% 2-H2BTB-3 4.0% 2-H2BTB-2 4.0% 3-HB(F)TB-2 3.0% 3-HB(F)TB-3 3.0% 3-HB(F)TB-4 3.0%

COMPOSITION EXAMPLE 47

2-HBCF2OBH-2 6.0% 3-HBCF2OBH-3 6.0% 3-HB(F,F)CF2OBH—V 3.0% 3-HB(F,F)CF2OBH-2V1 3.0% 2O1-BEB(F)—C 4.0% 3O1-BEB(F)—C 12.0% 5O1-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 15.0% 3-HHEB—F 5.0% 5-HHEB—F 5.0% 3-HBEB—F 6.0% 3-HHB—F 3.0% 3-HB—O2 10.0% 3-HH-4 5.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-HB(F)VB-2 5.0%

COMPOSITION EXAMPLE 48

3-HBCF2OB-3 7.0% 2-HB(F)CF2OBH-2V 3.0% 3-HB(F)CF2OBH-2V1 3.0% 3-HB(F,F)CF2OBTB-3 3.0% 2-HB(F)—C 15.0% 2-HEB—F 2.4 % 3-HEB—F 2.3 % 4-HEB—F 2.3 % 3-HHEB—F 4.0% 5-HHEB—F 4.0% 2-HHB(F)—C 12.0% 3-HHB(F)—C 12.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0%

COMPOSITION EXAMPLE 49

3-BCF2OBH-3 7.0% 2-BCF2OBH—V 7.0% 3-HB(F,F)CF2OBH—V1 3.0% 3-HB(F,F)CF2OBH-2V 3.0% 3-HB(F)—C 3.0% 3-HB—C 21.0% 3-HHB—C 5.0% 5-PyB—F 10.0% 3-HB—O2 4.0% 2-BTB-1 6.0% 3-HH-4 6.0% 3-HH-5 6.0% 3-HHB-1 5.0% 3-HHB-3 7.0% 3-HHB—O1 3.0% 3-HEBEB-2 2.0% 3-HEBEB—F 2.0%

COMPOSITION EXAMPLE 50

3-HBCF2OBH-3 8.0% 3-HBCF2OBH-5 8.0% 3-HB(F)CF2OBTB-3 4.0% 2-BB—C 8.0% 4-BB—C 6.0% 2-HB—C 10.0% 3-HB—C 13.0% 3-HHB—F 5.0% 2-HHB—C 4.0% 3-HHB—C 6.0% 5-PyB—F 6.0% 3-PyBB—F 6.0% 2-HHB-1 6.0% 3-HHB-3 5.0% 3-HHB—O1 5.0%

COMPOSITION EXAMPLE 51

5-HBCF2OB-3 8.0% 3-BCF2OBH—V 8.0% 3-HB(F)CF2OBH-3 6.0% 5-BB—C 8.0% 3-HHB—F 4.0% 3-HB—O2 12.0% 3-HB—O4 10.0% 3-PyB-4 2.5% 4-PyB-4 2.5% 6-PyB-4 2.5% 3-PyB-5 2.5% 4-PyB-5 2.5% 6-PyB-5 2.5% 6-PyB—O5 3.0% 6-PyB—O6 3.0% 6-PyB—O7 3.0% 6-PyB—O8 3.0% 2-HHB-1 4.0% 3-HHB-1 8.0% 3-HHB—O1 5.0%

COMPOSITION EXAMPLE 52

5-HBCF2OB-3 8.0% 5-HBCF2OBH-3 6.0% 3-H2BCF2OBH-3 6.0% 3-DB—C 10.0% 4-DB—C 12.0% 5-DB—C 8.0% 2-BEB—C 10.0% 5-PyB(F)—F 10.0% 2-PyB-2 1.4% 3-PyB-2 1.3% 4-PyB-2 1.3% 3-HEB—O4 2.2% 4-HEB—O2 1.6% 3-HEB—O2 1.3% 1O—BEB-2 1.1% 5-HEB-1 1.6% 4-HEB-4 2.2% 3-HHB-3 6.0% 3-HHB—O1 4.0% 2-PyBH-3 6.0%

COMPOSITION EXAMPLE 53

2-HBCF2OB-2 6.0% 3-HBCF2OB-3 4.0% 5-HBCF2OBH-3 6.0% 3-DB—C 10.0% 4-DB—C 10.0% 2-BEB—C 12.0% 3-BEB—C 4.0% 3-HHEBB—C 3.0% 3-HBEBB—C 3.0% 5-HBEBB—C 3.0% 3-PyB(F)—F 6.0% 3-HEB—O4 8.3% 4-HEB—O2 6.2% 5-HEB—O1 6.2% 3-HEB—O2 5.2% 5-HEB—O2 4.1% 3-HHB-1 3.0%

COMPOSITION EXAMPLE 54

3-H2BCF2OBH-3 5.0% 3-H2BCF2OBH-5 5.0% 5-HB—F 4.0% 7-HB—F 7.0% 3-HHB—OCF3 10.0% 5-HHB—OCF3 8.0% 3-H2HB—OCF3 6.0% 5-H2HB—OCF3 5.0% 2-HHB(F)—F 5.0.% 3-HHB(F)—F 5.0% 5-HHB(F)—F 5.0% 3-H2HB(F,F)—F 6.0% 4-H2HB(F,F)—F 5.0% 5-H2HB(F,F)—F 5.0% 3-HHB(F,F)—F 8.0% 3-HH2B(F,F)—F 6.0%

COMPOSITION EXAMPLE 55

5-HBCF2OB-3 8.0% 5-HBCF2OBH-3 6.0% 3-H2BCF2OBH-3 6.0% 7-HB—F 5.0% 3-HB—O2 4.0% 3-HHB—OCF3 10.0% 5-HHB—OCF3 5.0% 3-H2HB—OCF3 5.0% 5-H2HB—OCF3 5.0% 2-HHB(F)—F 7.0% 3-HHB(F)—F 7.0% 5-HHB(F)—F 7.0% 2-H2HB(F)—F 4.0% 3-H2HB(F)—F 2.0% 5-H2HB(F)—F 4.0% 2-HBB(F)—F 3.0% 3-HBB(F)—F 3.0% 5-HBB(F)—F 6.0% 3-HHB-1 3.0%

COMPOSITION EXAMPLE 56

3-BCF2OBH—V 6.0% 5-HBCF2OBH-3 4.0% V2-HB—C 9.0% 1V2-HB—C 9.0% 3-HB—C 14.0% 1O1-HB—C 8.0% 2O1-HB—C 4.0% 2-HHB—C 5.0% 3-HHB—C 5.0% V2-HH-3 10.0% 1O1-HH-5 4.0% 2-BTB—O1 8.0% V—HHB-1 5.0% V—HBB-2 5.0% 1V2-HBB-2 4.0%

COMPOSITION EXAMPLE 57

3-BCF2OBH—V 6.0% 3-H2BCF2OBH-3 7.0% 3-H2BCF2OBH-5 7.0% 2O1-BEB(F)—C 4.0% 3O1-BEB(F)—C 10.0% 5O1-BEB(F)—C 4.0% V—HB—C 10.0% 1V—HB—C 10.0% 3-HB—C 8.0% 2-HHB—C 4.0% 3-HHB—C 4.0% 4-HHB—C 4.0% 5-HHB—C 4.0% 3-HB—O2 5.0% V—HHB-1 5.0% V—HBB-2 4.0% 3-H2BTB-2 4.0%

COMPOSITION EXAMPLE 58

3-BCF2OBH-3 6.0% 5-HB(F,F)CF2OB-3 4.0% 3-HB(F)CF2OBH-3 5.0% 5-HB—F 6.0% 6-HB—F 4.0% 7-HB—F 7.0% 5-HB-3 3.0% 3-HB—O1 3.0% 2-HHB—OCF3 5.0% 3-HHB—OCF3 5.0% 4-HHB—OCF3 5.0% 5-HHB—OCF3 7.0% 3-HH2B—OCF3 2.0% 5-HH2B—OCF3 3.0% 3-HH2B—F 3.0% 5-HH2B—F 3.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 5.0% 3-HH2B(F)—F 7.0% 5-HH2B(F)—F 9.0% 5-HB(F)BH-3 2.0%

COMPOSITION EXAMPLE 59

3HB(F,F)CF2OBH-3 4.0% 2-BTB(F,F)CF2OBH-2 4.0% 2-HBCF2OBTB-2 8.0% 5-HB—F 7.0% 3-HH—O1 4.0% 3-HH—O3 4.0% 5-HH—O1 3.0% 3-HHB—OCF2 5.0% 5-HHB—OCF2 5.0% 3-HHB(F,F)—OCF2 8.0% 5-HHB(F,F)—OCF2 8.0% 2-HHB—OCHF3 5.0% 3-HHB—OCHF3 5.0% 4-HHB—OCHF3 5.0% 5-HHB—OCHF3 5.0% 3-HH2B(F)—F 7.0% 5-HH2B(F)—F 8.0% 3-HHEB(F)—F 5.0%

COMPOSITION EXAMPLE 60

2-BCF2OBH-2V 8.0% 3-HB(F)CF2OBH—V 6.0% 2-HB(F)CF2OBH-2V 6.0% V—HB—C 10.0% 1V-HB—C 5.0% 3-BB—C 5.0% 5-BB—C 5.0% 2-HB)F)—C 4.0% 4-BB-3 3.0% 3-H2B—O2 3.0% 5-H2B—O2 6.0% 3-BEB—C 5.0% 5-HEB—O1 6.0% 5-HEB—O3 6.0% 5-BBB—C 3.0% 4-BPyB—C 4.0% 4-BPyB-5 4.0% 5-HB2B-4 3.0% 5-HBB2B-3 2.0% 1V—HH-1O1 3.0% 1V2-HBB-3 3.0%

COMPOSITION EXAMPLE 61

3-BCF2OBH-2V1 6.0% 3-HB(F,F)CF2OBH-3 3.0% 2-BTB(F)CF2OBH-2 6.0% 4-HEB(F)—F 8.0% 5-HEB(F)—F 8.0% 2-BEB(F)—C 5.0% 3-BEB(F)—C 5.0% 4-BEB(F)—C 6.0% 5-BEB(F)—C 6.0% 1O3-HB(F)—C 6.0% 3-HHEB(F)—F 5.0% 5-HHEB(F)—F 5.0% 2-HBEB(F)—C 5.0% 3-HBEB(F)—C 5.0% 4-HBEB(F)—C 5.0% 5-HBEB(F)—C 5.0% 3-HBTB-2 5.0% V2-HH-3 3.0% V2-HHB-1 3.0%

Liquid crystalline compounds of the present invention expressed by the general formula (1) can readily produced by ordinary procedures in organic synthetic chemistry. For instance, the compounds can easily be produced by selecting proper procedures described in Organic Synthesis, Organic Reactions, Jikken Kagaku Kouza (Course of Chemical Experiment), or others and using them in combination.

For instance, compounds (1-A) expressed by the general formula (1) wherein m is 1, n is 0, and X² is —COO— can preferably be produced by the following method. That is, the compounds (1-A) can be produced by reacting carboxylic acid derivatives (13) with alcohol or phenol derivatives (14) in a solvent such as dichloromethane and chloroform in the presence of a dehydrating agent such as dicyclohexylcarbodiimide (DCC), and 4-dimethylaminopyridine (DMAP) (B. Neises et al., Organic Synthesis, 63, 183 (1985)).

wherein R¹, X¹, Y¹, and rings A¹, A², and A⁴ have the same meaning as described above.

Compounds (1-B) expressed by the general formula (1) wherein m is 1, n is 0, and X² is —CF₂O— can preferably be produced by the following method. That is, halides (15) are converted into Grignard reagents or lithiated compounds by using magnesium and lithium reagent, and then the reagents or lithiated compounds are reacted with carbon disulfide to produce dithiocarboxylic acid —derivatives (16). Subsequently, the derivatives (16) are reacted with thionyl chloride to convert into thioncarboxylic acid chloride, reacted with an alcohol or phenol to produce thion-O-ester derivatives (17), and then the derivatives (17) is reacted with diethylaminosulfur trifluoride (hereinafter abbreviated to DAST) or reacted with tetrabutylammonium dihydrogen trifluoride or HF-pyridine in the presence of an oxidizing agent such as N-bromosuccinimide (hereinafter abbreviated to NBS) and 1,3-dibromo-5,5-dimethylhidantoin (hereinafter abbreviated to DBH) according to a method described in Laid-open Japanese Patent Publication No. Hei 5-255165 to produce the objective compounds (1-B).

wherein R¹, X¹, Y¹, and rings A¹, A², and A⁴ have the same meaning as described above.

The thion-O-ester derivatives (17) can also be produced by deriving dithiocarboxylic acid derivatives (16) into alkali metal salts and then reacting with an alcolate or phenolate in the presence of iodine. Further, the ester derivatives (17) can be produced by reacting the ester derivatives (1-A) obtained by the production method described above with 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (hereinafter abbreviated to Lawesson's reagent).

Compounds expressed by the general formula (1) wherein X¹, X², or X³ is an ethenylene group, for example, compounds (1-C) expressed by the general formula (1) wherein m is 1, n is 0, X¹ is —CH═CH—, and X² is —CF₂O—, and compounds (1-D) wherein X² is —COO— can preferably be produced by the following method. That is, first, E,Z-olefin mixtures (22) are obtained by reacting ylides prepared by reacting the Wittig reagent (19), which can be prepared from bromomethane derivatives (18) and triphenylphosphine according to a method described in Organic Reactions, Vol. 14, Chapter 3, with a base such as a sodium alkoxide and an alkyl lithium in tetrahydrofuran (hereinafter abbreviated as THF) with aldehyde derivatives (21). Next, the E,Z-olefin mixtures are reacted with benzene sulfinic acid or p-toluenesulfinic acid according to a method described in Japanese patent publication No. Hei 4-30382 to isomerize. Alternatively, E,Z-olefin mixtures are reacted with m-chloroperbenzoic acid according to a method described in Japanese patent Publication No. Hei 6-62462 to convert into oxylane derivatives (23). The oxylane derivatives are then reacted with dibromotriphenyl phosphorane to derive into dibromo derivatives (24). Subsequently, the derivatives (24) are subjected to recrystallization to purify only erithro isomer and then reduced with metal zinc to produce E-olefin derivatives (25). The objective compounds (1-C) can be produced by treating the derivatives (25) in the same manner as in the compounds (I-B) described above.

wherein R¹, Y¹, and rings A¹, A², and A⁴ have the same meaning as described above.

On the other hand, carboxylic acid derivatives (26) can be produced by lithiating the compounds (25) obtained by the procedures described above with butyl lithium or the like, and then reacting with carbon dioxide. The objective compounds (1-D) can be produced by treating the compounds (26) in the same manner as in the case of producing compounds (1-C).

wherein R¹, Y¹, and rings A¹, A², and A⁴ have the same meaning as described above.

Compounds expressed by the general formula (1) wherein X¹, X², or X³ is ethynylene group, for examples, compounds (I-E) expressed by the general formula (1) wherein m is 1, n is 0, XI is —C≡C—, and X² is —CF₂O—, and compounds (1-F) wherein X² is —COO— can preferably be produced by the following methods. That 15 is, acetylene derivatives (27) are reacted with compounds (28) in the presence of a catalyst according to a method described in J. Org. Chem., 28, 2163, 3313 (1963) to produce compounds (29). The objective compounds (1-E) can be produced by treating the compounds (29) thus obtained in the same manner as in the case of producing the compounds (1-B) described above.

wherein R¹, Y¹, and rings A¹, A², and A⁴ have the same meaning as described above.

On the other hand, carboxylic acid derivatives (30) can be produced by lithiating the compounds (29) obtained by the procedures described above with butyl lithium or the like, and then reacting with carbon dioxide. The objective compounds (1-F) can be produced by treating the compounds (30) in the same manner as in the case of producing the compounds (1-C) described above.

wherein R¹, X¹, Y¹, and rings A¹, A², and A⁴ have the same meaning as described above.

Acetylene derivatives (27) can readily be produced by treating dibromides (31), which can easily be produced by adding bromine to corresponding vinyl derivatives, with a base according to a method described in J. Org. Chem., 38, 1367 (1963).

wherein R¹ and ring A¹ have the same meaning as described above.

Besides, other compounds which are not described above can preferably be produced by properly selecting various methods described in well known reference books on organic synthesis or patent publications and combining the methods.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the methods for producing the compounds of the present invention and the methods for using the compounds are described in more detail with reference to Examples. In each of the Examples, Cr indicates crystal; N, nematic phase; Sm, smectic phase; and Iso, isotropic liquid, and the unit of all phase transition temperatures is ° C. In ¹H-NMR, s indicates singlet; d, doublet; t, triplet; and m, multiplet; and J indicates coupling constant (Hz). Further, in mass spectrum (GC-MS), M⁺indicates molecular ion peak.

EXAMPLE 1

Preparation of 2,3-difluoro-4-ethoxyphenyl 2-fluoro-4-(2-(trans-4-propylcyclohexyl)ethyl)benzoate (Compound expressed by the general formula (1) wherein m is 1, n is 0, ring A¹ represents trans-1,4-cyclohexylene group, ring A² represents 2fluoro-1,4-phenylene group, ring A⁴ represents 2,3-difluoro-1,4-phenylene group, X¹ represents —CH₂CH₂-, R¹ represents n—C₃H₇, and Y¹ represents OC₂H₅; Compound No. 15)

(First step)

First, 100 g (0.77 mol) of 2,3-difluorophenol, 100 g (0.92 mol) of ethyl bromide, 127 g (0.92 mol) of potassium carbonate, 1.0 g (6.0 mmol) of potassium iodide, and 1.3 l of dimethyl-formamide (DMF) were mixed and heated to reflux for 7 hours. After finishing of the reaction, 1.0 l of water was added to the reaction solution and then extracted with 2.0 l of toluene. The organic layer thus obtained was washed with water once and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was distilled under a reduced pressure to obtain 87.5 g of 2,3-difluoroethoxybenzene (yield 71.4%).

(Second step)

To a solution prepared by dissolving 19.0 g (0.12 mol) of the 2,3-difluoroethoxybenzene obtained by the first step, in 250 ml of tetrahydrofuran (THF) was added dropwise 100 ml of solution of 1.56 M of n-butyl lithium in hexane at −78° C. in 30 min and stirred as it was for 30 min. To this solution was added dropwise solution of 25 g (0.24 mol) of trimethyl borate in 50 ml of THF at the same temperature in 10 min, stirred at the same temperature for 3 hours, and then gradually warmed up to room temperature. To this solution was added 55.2 g (1.2 mol) of formic acid, further 108.8 g of 30% by weight of hydrogen peroxide was added in 30 min, and then the solution was heated up to 50° C. and stirred as it was for 30 min. After the reaction solution was allowed to stand to cool down to room temperature, the solution was poured into 5% by weight of aqueous sodium thiosulfate solution and extracted with 400 ml of toluene. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under a reduced pressure, and the residue was recrystallized from heptane to obtain 9.1 g of 2,3-difluoro-4-ethoxyphenol (yield 43.4%).

(Third step)

First, 1.7 g (10 mmol) of the 2,3-difluoro-4-ethoxyphenol obtained by the second step, 2.9 g (10 mmol) of 2-fluoro-4-(2-(trans-4-propylcyclohexyl)ethyl)benzoic acid, 1.3 g (11 mmol) of DMAP, and 100 ml of dichloromethane were mixed. To this mixture was added dropwise solution of 2.27 g (11 mmol) of DCC in 15 ml of dichloromethane under a condition cooled with ice in 10 min, and then the mixture was warmed up to room temperature and stirred as it was overnight. Separated crystals were filtered off and the solvent was distilled off under a reduced pressure from the filtrate. The residue was purified by silica gel column chromatography (eluent: ethyl acetate) and further recrystallized from heptane to obtain 2.48 g of the subject compound (yield 55.3%).

This compound exhibited liquid crystal phase and its phase transition temperatures were as follows:

C-N point: 65.4, N-I point: 141.3

Data of various kind of spectrums supported the structure of the compound described above.

¹H-NMR (CDCl₃) δ (ppm): 8.09-7.92 (t, 1H, J=15.7 Hz), 7.11-6.75 (m, 4H), 4.25-4.02 (q, 2H, J=21.2 Hz), 2.78-2.61 (t, 2H, J=15.7 Hz), 1.81-0.88 (m, 22H)

Mass spectrum: 448 (M⁺)

EXAMPLE 2

Preparation of (2,3-difluoro-4-ethoxyphenyl)oxy(4-(trans-4-n-pentylcyclohexyl)phenyl)difluoromethane (Compound expressed by the general formula (1) wherein m is 1, n is 0, ring A¹ represents trans-1,4-cyclohexylene group, ring A² represents 1,4-phenylene group, ring A⁴ represents 2,3-difluoro-1,4-phenylene group, X¹ represents single bond, X² represents —CF₂O—, R¹ represents n-C₅H₁₁, and Y¹ represents OC₂H₅; Compound No. 152)

(First step)

To a suspension prepared by suspending 0.95 g (39 mmol) of magnesium in 200 ml of THF was added dropwise a solution prepared by dissolving 9.28 g (30 mmol) of 4-(trans-4-n-pentylcyclohexyl)bromobenzene in 80 ml of THF, at room temperature while being stirred in 1 hour, and then heated to reflux for 2 hours to prepare a Grignard reagent. To this solution was added dropwise 5.7 g (75 mmol) of carbon disulfide at room temperature in 30 min and stirred as it was overnight. To this reaction solution was added 150 ml of 1M hydrochloric acid to terminate the reaction and extracted with 350 ml of toluene. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under a reduced pressure, and the residue was recrystallized from heptane to obtain 4.74 g of 4-(trans-4-n-pentylcyclohexyl)phenyldithiocarboxylic acid (yield 51.5%).

(Second step)

To a suspension prepared by suspending 1.52 g (38.0 mmol) of 60% sodium hydride in 15 ml of THF was added dropwise solution of 5.29 g (17.3 mmol) of the 4-(transs-4-n-pentylcyclohexyl)phenyldithiocarboxylic acid obtained by the first step, in 20 ml of THF under a condition cooled with ice in 15 min, and stirred as it was for 30 min. To this reaction solution was added dropwise solution of 2.50 g (14.4 mmol) of 2,3-difluoro-4-ethoxyphenol in 20 ml of THF in 15 min and stirred as it was for 30 min. To this reaction solution was added dropwise solution of 9.64 g (38.0 mmol) of iodine in 20 ml of THF in 15 min, stirred as it was for 1 hour, warmed up to room temperature, and then stirred at the same temperature overnight. This reaction solution was poured into 10% aqueous sodium thiosulfate solution and extracted with 100 ml of diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under a reduced pressure, and the residue was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 2.0 g of 2,3-difluoro-4-ethoxyphenyl 4-(trans-4-n-pentylcyclohexyl)thiobenzoate (yield 31.2%).

(Third step)

To a suspension prepared by suspending 1.59 g (8.93 mmol) of N-bromosuccinimide in 20 ml of methylene chloride was added dropwise 1.78 g of hydrogen fluoride-pyridine at −78° C. in 15 min and stirred as it was for 10 min. To this reaction solution was added dropwise solution of 2.0 g (4.48 mmol) of 2,3-difluoro-4-ethoxyphenyl 4-(trans-4-n-pentylcyclohexyl)thiobenzoate in 30 ml of methylene chloride in 30 min and stirred as it was for 2 hours. This reaction solution was poured into saturated aqueous sodium carbonate solution to terminate the reaction. The methylene chloride layer was separated, and washed with 10% aqueous sodium bisulfite solution and water in turn, and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was purified by silica gel column chromatography (eluent: heptane) to obtain 0.72 g of the subject compound (yield 35.5%).

This compound exhibited liquid crystal phase and its phase transition temperatures were as follows:

C-N point: 61.4, N-I point: 131.4

Data of various kind of spectrums supported the structure of the compound described above.

¹H-NMR (CDCl₃) δ (ppm): 7.71-6.57 (m, 6H), 4.26-4.00 (q, 2H, J=21.0 Hz), 2.53-2.83 (m, 24H)

¹⁹F-NMR (CDCl₃) δ (ppm): −66.5 (s, —CF₂O—)

Mass spectrum: 452 (M⁺)

EXAMPLE 3

Preparation of difluoro-(4-pentylphenyloxy) (4-(trans-4-propylcyclohexyl)phenyl)methane (Compound expressed by the general formula (1) wherein m is 1, n is 0, ring A¹ represents trans-1,4-cyclohexylene group, ring A² represents 1,4-phenylene group, ring A⁴ represents 1,4-phenylene group, X¹ represents single bond, X² represents —CF₂O—, R¹ represents n—C₃H₇, and Y¹ represents C₅H₁₁; Compound No. 331)

(First step)

In a 500 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 2.7 g (112.1 mmol) of turnings of magnesium were suspended in 50 ml of THF while being stirred under nitrogen gas atmosphere, and 70 ml of solution of 30 g (106.8 mmol) of 4-(trans-4-propylcyclohexyl)bromobenzene in THF was added dropwise in 40 min so that the internal temperature did not exceed 50° C. The reaction solution was stirred while being heated at 50° C. with a hot water bath for 2 hours to age. After the solution was cooled with an ice bath to lower the internal temperature down to 5° C., 24.4 g (320.4 mmol) of carbon disulfide was added dropwise in 25 min so that the internal temperature did not exceed 10° C. The reaction solution was stirred while being maintained at a temperature lower than 10° C. for 30 min, warmed up to room temperature, and then stirred for 1 hour. The reaction solution was cooled down to a temperature lower than 5° C. again, 25 ml of 6N hydrochloric acid was added thereto to terminate the reaction, and then extracted with 400 ml of diethyl ether. The organic layer was washed with 300 ml of an ice water and dried over anhydrous magnesium sulfate. Diethyl ether was distilled off and the residue was concentrated to obtain 23.7 g of a deep purplish red (murex) solid. This product was 4-(trans-4-propylcyclohexyl)phenyldithiocarboxylic acid.

(Second step)

In a 500 ml eggplant type flask, 23.7 g of the 4-(trans-4-propylcyclohexyl)phenyldithiocarboxylic acid obtained by the procedures described above was dissolved in 200 ml of diethyl ether, 50.8 g of thionyl chloride was added thereto, and then the solution was heated on a hot water bath to reflux for 8 hours. The diethyl ether and unreacted thionyl chloride were distilled off under a reduced pressure produced with an aspirator, and the residue was concentrated to obtain 25 g of a deep murex oily substance. This substance was thioncarboxylic acid chloride derivative. Subsequently, in a 500 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 21.0 g (128.2 mmol) of 4-pentylphenol and 10.1 g (128.1 mmol) of pyridine were dissolved in 30 ml of toluene under nitrogen gas atmosphere, and 70 ml of solution of 25.0 g of the thioncarboxylic acid chloride derivative obtained by the procedures described above in toluene was added thereto while being stirred the solution at room temperature in 20 min. After finishing of the dropping, the reaction solution was heated on a hot water bath so that the internal temperature rose up to 60° C. and then stirred for 3 hours to age. After the reaction solution was cooled down to room temperature, 100 ml of water and 30 ml of 6N hydrochloric acid were added to the reaction solution, the toluene layer was separated, and then the water layer was extracted with 200 ml of toluene. The toluene layers were coalesced, washed with 200 ml of water, 80 ml of 2N aqueous sodium hydroxide solution, and 300 ml of water in turn, and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure to obtain 28.3 g of a deep murex past like residue. The residue was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 12.7 g of pale yellow needle-shaped crystals of 4-pentylphenyl 4-(trans-4-n-propylcyclohexyl)thiobenzoate.

(Third step)

In a 300 ml eggplant type flask, 5.0 g (12.3 mmol) of the 4-pentylphenyl 4-(trans-4-n-propylcyclohexyl)thiobenzoate obtained by the procedures described above was dissolved in 60 ml of dichloromethane under nitrogen gas stream, 7.9 g (49.0 mmol) of DAST was added thereto at room temperature, and then the solution was stirred for 25 hours. The reaction solution was added to 200 ml of an ice water to terminate the reaction, the dichloromethane layer was separated, and further the water layer was extracted with 100 ml of dichloromethane. The dichloromethane layers were coalesced, washed with 200 ml of water, 50 ml of 2N aqueous sodium hydroxide solution, and 200 ml of water in turn, and then dried over anhydrous magnesium sulfate. The dichloromethane was distilled off and the residue was concentrated to obtain 3.8 g of a pale yellow crystalline crude product. This crude product was purified by silica gel column chromatography (eluent: heptane) and then recrystallized from heptane to obtain 1.7 g of colorless needle-shaped crystals of difluoro-(4-pentylphenyloxy) (4-(trans-4-propylcyclohexyl)phenyl)methane. Data of various kind of spectrums supported the structure of the compound described above.

Mass spectrum: 414 (M⁺)

EXAMPLE 4

Preparation of difluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy) (4-propylphenyl)methane (Compound expressed by the general formula (1) wherein m is 1, n is 0, both ring A¹ and ring A² represent 1,4-phenylene group, ring A⁴ represents trans-1,4-cyclohexylene group, X¹ represents —CF₂O—, X² represents single bond, R¹ represents n—C₃H₇, and Y¹ represents vinyl group; Compound No. 441)

Preparation process can broadly be divided into three stages of 1) synthesis of 4-(4-hydroxyphenyl)cyclohexanone, 2) synthesis of cyclohexanone intermediate (32), and 3) preparation of difluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy) (4-propylphenyl)methane. The process is described in detail below with each preparation stage being separated.

1) [Synthesis of 4-(hydroxyphenyl)cyclohexanone]

(First step)

In a 1 l three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 5.8 g (239.0 mmol) of turnings of magnesium were suspended in 100 ml of THF while being stirred under nitrogen gas atmosphere, and 200 ml of solution of 60 g (228.1 mmol) of 4-bromophenoxybenzyl ether in THF was added dropwise thereto in 80 min so that the internal temperature did not exceed 50° C. The reaction solution was stirred while being heated at 50° C. with a hot water bath for 2 hours to age. Subsequently, 42.7 g (274.3 mmol) of 1,4-cyclohexanedionemonoethyleneketal was added dropwise at room temperature to the reaction solution in 40 min so that the internal temperature did not exceed 60° C. The reaction solution was stirred on a hot water bath while being maintained at 50° C. for 2 hours and then cooled with an ice water, and 100 ml of saturated aqueous ammonium chloride solution was added thereto to terminate the reaction. The reaction solution was extracted with 400 ml of toluene. The toluene extract was washed with 900 ml of water and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure to obtain 73.6 g of a brown solid product. This product was dissolved in 340 ml of toluene in a 1 l eggplant type flask provided with a Dean and Stark dehydrating tube, 5.9 g of non-aqueous acidic ion exchange resin (Amberlist) was added as acid catalyst thereto, and the solution was heated to reflux for 3 hours while being stirred. After the catalyst was removed by filtration, the toluene was distilled off under a reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene), and then recrystallized from toluene to obtain 41.8 g of colorless needle-shaped crystals of cyclohexene derivative (33).

(Second step)

The cyclohexene derivative (33) obtained in the first step was dissolved in 200 ml of mixed solvent of toluene/ethanol of 1/1 in a 1 l eggplant type flask, 2.5 g of 5% palladium-carbon catalyst was added thereto, and the solution was subjected to a hydrogenation reaction at room temperature under a hydrogen gas pressure of 1 to 2 kg/cm² for 6 hours. After the catalyst was removed by filtration, the reaction solution was concentrated to obtain 30.2 g of a reaction product. This reaction product was dissolved in 100 ml of toluene in a 300 ml three-necked flack provided with a stirrer and thermometer, 29.9 g of 99% formic acid was added to the solution, and then the solution was heated to reflux while being stirred for 2 hours. Water in an amount of 300 ml was added to the reaction solution, the toluene layer was separated, and further the water layer was extracted with 200 ml of toluene. The toluene layers were coalesced, washed with 800 ml of water, and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure to obtain 18.0 g of 4-(4-hydroxyphenyl)cyclohexanone.

2) [Synthesis of cyclohexanone intermediate (32)]

(Third step)

In a 300 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 18.0 g (94.8 mmol) of 4-(4-hydroxyphenyl)cyclohexanone was dissolved in 30 ml of toluene under nitrogen gas atmosphere, 9.7 g (123.0 mmol) of pyridine was added thereto, and then 50 ml of solution of 24.4 g (123.0 mmol) of the 4-propylphenylthioncarboxylic acid chloride synthesized by the same procedures as in the first and second steps in Example 1, in toluene was added dropwise in 15 min. After finishing of the dropping, the reaction solution was heated up to 60° C. on a hot water bath and stirred for 3 hours to age. After the reaction solution was cooled down to room temperature, 100 ml of water and 50 ml of 6N hydrochloric acid were added thereto, the toluene layer was separated, and then the water layer was extracted with 200 ml of toluene. The toluene layers were coalesced, washed with 200 ml of water, 50 ml of 2N aqueous sodium hydroxide solution, and 300 ml of water in turn, and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure to obtain 33.2 g of a deep murex paste like product. This product was purified by silica gel column chromatography (eluent: mixed solvent of heptane/toluene=1/1) and further recrystallized from heptane to obtain 18.4 g of pale yellow needle-shaped crystals. These crystals were thioncarboxylic acid—O—ester derivative (34).

(Fourth step)

In a 300 ml eggplant type flask provided with a nitrogen gas inlet tube, 18.4 g (52.0 mmol) of the thioncarboxylic acid—O— ester derivative (34) obtained by the procedures described above was dissolved in 250 ml of dichloromethane under nitrogen gas atmosphere, 33.5 g (208.0 mmol) of DAST was added thereto at room temperature, and then the solution was stirred for 25 hours. The reaction solution was added to 200 ml of an ice water to terminate the reaction, the dichloromethane layer was separated, and further the water layer was extracted with 100 ml of dichloromethane. The dichloromethane layers were coalesced, washed with 200 ml of water, 50 ml of 2N aqueous sodium hydroxide solution, and 200 ml of water in turn, and then dried over anhydrous magnesium sulfate. The dichloromethane was distilled off to obtain 13,6 g of a pale yellow crystalline crude product. This crude product was purified by silica gel column chromatography (eluent: mixed solvent of heptane/toluene=1/1) and further recrystallized from heptane to obtain 8.0 g of colorless needle-shaped crystals. These crystals were cyclohexanone intermediate (32).

3) [Synthesis of difluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy) (4-propylphenyl)methane]

(Fifth step)

In a 300 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 9.8 g (28.6 mmol) of methoxymethyltriphenylphosphonium chloride was dissolved in 80 ml of THF under nitrogen gas atmosphere and cooled down to a temperature lower than −50° C. with a dry ice-acetone bath, 3.4 g (30.0 mmol) of potassium-t-butoxide was added thereto, and then the solution was stirred while being maintained at a temperature lower than −50° C. for 2 hours to prepare an ylide. Then, 20 ml of solution of 8.0 g (22.0 mmol) of the cyclohexanone intermediate (32) obtained by the fourth step described above, in THF was added thereto at the same temperature in 10 min, and stirred at the same temperature for 1 hour. Subsequently, the solution was warmed up to room temperature and further stirred at room temperature for 8 hours. After 200 ml of water was added to the reaction solution to terminate the reaction, the THF layer was separated, and further the water layer was extracted with 100 ml of toluene. The toluene layers were coalesced, washed with 500 ml of water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain 18.5 g of a crude product. This crude product was purified by silica gel column chromatography (eluent: toluene) to obtain 7.6 g of a yellowish brown product. The product thus obtained was dissolved in 50 ml of toluene in a 200 ml eggplant type flask, 5.3 g (114.0 mmol) of 99% formic acid was added thereto, and the solution was heated to reflux for 2 hours. Water in an amount of 50 ml was added to the reaction solution and extracted with 50 ml of toluene. The toluene layer was washed with 100 ml of water, 30 ml of 2N aqueous sodium hydroxide solution, and 100 ml of water in turn, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and 7.3 g of the residue thus obtained was purified by silica gel column chromatography (eluent: toluene) to obtain 5.6 g of colorless crystalline cyclohexanecarbaldehyde derivative (35).

(Sixth step)

In a 200 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 7.0 g (17.4 mmol) of methyltriphenylphosphonium iodide was suspended in 30 ml of THF under nitrogen gas atmosphere and cooled down to a temperature lower than −50° C. with a dry ice-acetone bath, and 2.1 g (18.3 mmol) of potassium-t-butoxide was added thereto, and then the suspension was stirred while being maintained at a temperature lower than −50° C. for 2 hours to prepare a ylide. Then, 15 ml of solution of 5.0 g (13.4 mmol) of the cyclohexanecarboaldehyde derivative (35) obtained by the fifth step, in THF was added dropwise thereto at the same temperature in 5 min, stirred at the same temperature for 1 hour, warmed up to room temperature, and further stirred for 8 hours. Water in an amount of 50 ml was added to the reaction solution to terminate the reaction, the THF layer was separated, and further the water layer was extracted with 50 ml of toluene. The THF layer and the toluene layer were coalesced, washed with 80 ml of water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and 4.8 g of the product thus obtained was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 2.4 g of a colorless needle-shaped compound. This compound was the objective difluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy) (4-propylphenyl)methane. Data of various kind of spectrums supported the structure of the compound described above.

Mass spectrum: 370 (M⁺)

EXAMPLE 5

Preparation of difluoro-(4-(trans-4-(3-butenyl)cyclohexyl)phenyloxy) (4-propylphenyl)methane (Compound expressed by the general formula (1) wherein m is 1, n is 0, both ring A¹ and ring A² represent 1,4-phenylene group, ring A⁴ represents trans-1,4-cyclohexylene group, X¹ represents —CF₂O—, X² represents single bond, R¹ represents n—C₃H₇, and Y¹ represents 3-butenyl; Compound No. 442)

(First step)

In a 100 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 12.8 g (29.1 mmol) of 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide was suspended in 40 ml THF under nitrogen gas atmosphere and cooled down to a temperature lower than -50° C. with a dry ice-acetone bath, 3.4 g (30.5 mmol) of potassium-t-butoxide was added to the suspension, and then the suspension was stirred while being maintained at a temperature lower than −50° C. for 2 hours to prepare a ylide. Then, 30 ml of solution of 8.0 g (22.4 mmol) of the cyclohexanone intermediate (32) described in Example 4, in THF was added dropwise thereto at the same temperature in 20 min, stirred at the same temperature for 1 hour, warmed up to room temperature, and further stirred for 8 hours. Water in an amount of 50 ml was added to the reaction solution to terminate the reaction, the THF layer was separated, and the water layer was extracted with 100 ml of toluene. The THF layer and the toluene layer were coalesced, washed with 200 ml of water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and 15.5 g of the residue thus obtained was purified by silica gel column chromatography (eluent: mixed solvent of toluene/ethyl acetate) to obtain 8.2 g of yellowish brown crystals. Subsequently, these yellowish brown crystals were dissolved in 60 ml of mixed solvent of toluene/ethanol of 1/1 in a 200 ml eggplant type flask, 0.4 g of 5% palladium-carbon catalyst was added thereto, and then the solution was subjected to a catalytic hydrogen reduction at room temperature under a condition of hydrogen gas pressure of 1 to 2 kg/cm² until the time when absorption of hydrogen ceased. The catalyst was removed from the reaction solution by filtration and then the solvent was distilled off under a reduced pressure to obtain 7.4 g of a product. This product was dissolved in 30 ml of toluene in a 100 ml of eggplant type flask, 3.9 g (83.5 mmol) of 99% formic acid was added thereto, and then the solution was heated to reflux for 2 hours. Water in an amount of 50 ml was added to the reaction solution, the toluene layer was separated, and further the water layer was extracted with 60 ml of toluene. The toluene layers were coalesced, washed with 100 ml of water, 30 ml of 2N aqueous sodium hydroxide solution, and 100 ml of water in turn, and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure, and 7.0 g of the residue thus obtained was purified by silica gel column chromatography (eluent: toluene) to obtain 5.9 g of yellowish brown crystalline aldehyde derivative (36).

(Second step)

In a 100 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 7.8 g (19.3 mmol) of methyltriphenylphosphonium iodide was suspended in 30 ml of THF under nitrogen gas atmosphere and cooled down to a temperature lower than −50° C. with a dry ice-acetone bath, 2.2 g (20.3 mmol) of potassium-t-butoxide was added thereto, and then the suspension was stirred while being maintained at a temperature lower than −50° C. for 2 hours to prepare a ylide. Then, 20 ml of solution of 5.9 g (14.9 mmol) of the aldehyde derivative (36) obtained by the first step, in THF was added dropwise at the same temperature thereto in 5 min, stirred at the same temperature for 1 hour, warmed up to room temperature, and further stirred for 8 hours. Water in an amount of 50 ml was added to the reaction solution to terminate the reaction, the THF layer was separated, and the water layer was extracted with 100 ml of toluene. The THF layer and the toluene layer were coalesced, washed with 200 ml of water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and 5.6 g of the product thus obtained was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 2.4 g of colorless needle-shaped crystals. These crystals were the objective difluoro-(4-(trans-4-(3-butenyl)cyclohexyl)phenyloxy) (4-propylphenyl)methane. Data of various kind of spectrums supported the structure of the compound described above.

Mass spectrum: 398 (M⁺)

EXAMPLE 6

Preparation of difluoro-(4-(trans-4-propylcyclohexyl)phenyloxy) (4-(trans-4-pentylcyclohexyl)phenyl)methane (Compound expressed by the general formula (1) wherein m and n are 1, both ring A¹ and ring A⁴ represent trans-1,4-cyclohexylene group, both A² and ring A³ represent 1,4-phenylene group, both X¹ and X³ represent single bond, X² represents —CF₂O—, R¹ represents n—C₅H₁₁, and Y¹ represents n—C₃H₇; Compound No. 572)

(First step)

In a 500 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 4.2 g (172.7 mmol) of turnings of magnesium were suspended in 50 ml of THF under nitrogen gas atmosphere, and 120 ml of solution of 50 g (161.7 mmol) of 4-(trans-4-pentylcyclohexyl)bromobenzene in THF was added dropwise thereto while the internal temperature being maintained at 50° C. on a hot water bath in 40 min. The reaction solution was stirred while being heated at 50° C. with a hot water bath for 2 hours to age. Then, the contents of the flask were cooled with an ice bath so that the internal temperature lowered down to 5° C., and 61.6 g (809.0 mmol) of carbon disulfide was added dropwise in 35 min so that the internal temperature did not exceed 10° C. The reaction solution was stirred while being maintained at a temperature lower than 10° C. for 30 min, warmed up to room temperature, and then stirred for 2 hours. The reaction solution was cooled down again to a temperature lower than 5° C., 100 ml of 6N hydrochloric acid was added thereto to terminate the reaction, and then extracted with 800 ml of diethyl ether. The diethyl ether layer was washed with 800 ml of an ice water and then dried over anhydrous magnesium sulfate. The diethyl ether was distilled off to obtain 50.8 g of a deep murex solid. This solid was 4-(trans-4-pentylcyclohexyl)phenyl-dithiocarboxylic acid.

(Second step)

In a 500 ml eggplant type flask, 50.8 g of the 4-(trans-4-pentylcyclohexyl)phenyldithiocarboxylic acid obtained by the procedures described above was dissolved in 300 ml of diethyl ether, 115.6 g (971.6 mmol) of thionyl chloride was added thereto at room temperature, and then the solution was heated on a hot water bath to reflux for 8 hours. The diethyl ether and unreacted thionyl chloride were distilled off under a reduced pressure produced with an aspirator to obtain 66.8 g of a deep murex paste like substance. This substance was thioncarboxylic acid chloride derivative.

Subsequently, in a 500 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 17.2 g (78.8 mmol) of 4-(trans-4-propylcyclohexyl)phenol and 5.7 g (72.2 mmol) of pyridine were dissolved in 80 ml of toluene under nitrogen gas atmosphere, and 60 ml of solution of 20.3 g of the thioncarboxylic acid chloride derivative obtained by the procedures described above, in toluene was added dropwise thereto in 20 min. After finishing of the dropping, the reaction solution was heated up to 60° C. on a hot water bath and stirred for 3 hours to age. After the reaction solution was cooled down to room temperature, 200 ml of water and 80 ml of 6N hydrochloric acid were added to the reaction solution, the toluene layer was separated, and further the water layer was extracted with 300 ml of toluene. The toluene layers were coalesced, washed with 400 ml of water, 80 ml of 2N aqueous sodium hydroxide solution, and 400 ml of water in turn, and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure, and 31.9 of a deep murex paste like product thus obtained was purified by silica gel column chromatography (eluent: mixed solvent of heptane/toluene) and recrystallized from heptane to obtain 5.8 g of pale yellow needle-shaped crystals. These crystals were thioncarboxylic acid—O—ester derivative (37).

Phase transition temperatures: Cr 136.2 N 263.6 Iso

¹H-NMR δ (ppm): 0.8-2.1 (36H, m), 2.3-2.7 (2H, m), 7.0 (2H, d, J=8.6 Hz), 7.2-7.3 (4H, bd), and 8.3 (2H, d, J=8.3 Hz)

(Third step)

In a 100 ml eggplant type flask, 5.8 g (11.9 mmol) of the thioncarboxylic acid—O—ester derivative (37) obtained by the procedures described above was dissolved in 60 ml of dichloromethane under nitrogen gas stream, and 9.6 g (59.5 mmol) of DAST was added thereto at room temperature and stirred for 25 hours. The reaction solution was added to 200 ml of an ice water to terminate the reaction, the dichloromethane layer was separated, and further the water layer was extracted with 100 ml of dichloromethane. The dichloromethane layers were coalesced, washed with 200 ml of water, 50 ml of 2N aqueous sodium hydroxide solution, and 200 ml of water in turn, and then dried over anhydrous magnesium sulfate. The dichloromethane was distilled off, and 7.6 g of a pale yellow crystalline mixture thus obtained was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 1.9 g of colorless needle-shaped crystals. These crystals were the objective difluoro-(4-(trans-4-propylcyclohexyl)phenyloxy) (4-(trans-4-pentylcyclohexyl)phenyl)methane. Data of various kind of spectrums supported the structure of the compound described above.

Phase transition temperatures: S_(A)106.3 N˜170.0 Iso (decomposed)

¹H-NMR δ (ppm): 0.8-2.1 (36H, m), 2.3-2.8 (2H, m), 7.2 (4H, S), 7.2-7.3 (2H, bd), and 7.6 (2H, d, J=8.3 Hz)

Mass spectrum: 496 (M⁺)

EXAMPLE 7

Preparation of difluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy) (4-(trans-4-propylcyclohexyl)phenyl)methane (Compound expressed by the general formula (1) wherein m and n are 1, both ring A¹ and ring A⁴ represent trans-1,4-cyclohexylene group, both ring A² and ring A³ represent 1,4-phenylene group, both X¹ and X³ represent single bond, X² represents —CF₂O—, R¹ represents n—C₃H₇, and Y¹ represents vinyl group; Compound No. 573)

(First step)

In a 500 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 14.1 g (74.3 mmol) of the 4-(4-hydroxyphenyl)cyclohexanone prepared by Example 4 (first and second steps) and 7.4 g (93.7 mmol) of pyridine were dissolved in 50 ml of toluene under nitrogen gas atmosphere, and 60 ml of solution of 25.0 g (89.2 mmol) of the thioncarboxylic acid chloride derivative prepared by Example 3 (first and second steps), in toluene was added dropwise while being stirred at room temperature in 20 min. After finishing of the dropping, the reaction solution was heated up to 60° C. on a hot water bath and stirred for 3 hours to age. The reaction solution was cooled down to room temperature, 200 ml of water and 80 ml of 6N hydrochloric acid were added to the solution, the toluene layer was separated, and further the water layer was extracted with 300 ml of toluene. The toluene layers were coalesced, washed with 400 ml of water, 80 ml of 2N aqueous sodium hydroxide solution, and 400 ml of water in turn, and then dried over anhydrous magnesium sulfate. The toluene was distilled off under a reduced pressure, and 38.2 g of the deep murex paste like product thus obtained was purified by silica gel column chromatography (eluent: mixed solvent of heptane/toluene) and further recrystallized from heptane to obtain 14.3 g of pale yellow needle-shaped crystals. These crystals were thioncarboxylic acid—O—ester derivative (38).

(Second step)

In a 100 ml eggplant type flask, 14.3 g (32.9 mmol) of the thioncarboxylic acid-O-ester derivative (38) obtained by the procedures described above was dissolved in 100 ml of dichloromethane under nitrogen gas atmosphere, and 26.5 g (164.7 mmol) of DAST was added thereto at room temperature and stirred for 25 hours. The reaction solution was added to 300 ml of an ice water to terminate the reaction, the dichloromethane layer was separated, and further the water layer was extracted with 200 ml of dichloromethane. The dichloromethane layers were coalesced, washed with 500 ml of water, 80 ml of 2N aqueous sodium hydroxide solution, and 500 ml of water in turn, and then dried over anhydrous magnesium sulfate. The dichloromethane was distilled off, and 14.1 g of a pale yellow crystalline mixture thus obtained was purified by silica gel column chromatography (eluent: toluene) and further recrystallized from heptane to obtain 7.1 g of colorless needle-shaped crystals. These crystals were cyclohexanone derivative (39).

(Third step)

In a 300 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 6.9 g (20.1 mmol) of methoxymethyl-triphenylphosphonium chloride was suspended in 50 ml of THF under nitrogen gas atmosphere and cooled down to a temperature lower than −50° C. with a dry ice-acetone bath, 2.4 g (21.1 mmol) of potassium-t-butoxide was added thereto, and then the suspension was stirred while being maintained at a temperature lower than −50° C. for 2 hours to prepare a ylide. Then, 20 ml of solution of 7.1 g (16.1 mmol) of the cyclohexanone derivative (39) obtained by the second step, in THF was added dropwise thereto in 10 min at the same temperature, stirred at the same temperature for 1 hour, warmed up to room temperature, and then further stirred for 8 hours. Water in an amount of 100 ml was added to the reaction solution to terminate the reaction, the THF layer was separated, and further the water layer was extracted with 100 ml of toluene. The THF layer and the toluene layer were coalesced, washed with 200 ml of water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and 14.1 g of the product thus obtained was purified by silica gel column chromatography (eluent: toluene) to obtain 6.8 g of a yellowish brown reaction product.

Subsequently, in a 200 ml eggplant type flask, the reaction product was dissolved in 40 ml of toluene, 4.1 g (88.2 mmol) of 99% formic acid was added thereto, and the solution was heated to reflux for 2 hours. Water in an amount of 50 ml was added to the reaction solution and extracted with 50 ml of toluene, the extract layer was washed with 100 ml of water, 30 ml of 2N aqueous sodium hydroxide solution, and 100 ml of water in turn, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and 9.8 g of the product thus obtained was purified by silica gel column chromatography (eluent: toluene) to obtain 4.7 g of colorless crystals. These crystals were cyclohexanecarbaldehyde derivative (40).

(Fourth step)

In a 200 ml three-necked flask provided with a stirrer, thermometer, and nitrogen gas inlet tube, 5.2 g (12.9 mmol) of methyltriphenylphosphonium iodide was suspended in 30 ml of THF under nitrogen gas atmosphere and cooled down to a temperature lower than −50° C. with a dry ice-acetone bath, 1.5 g (13.5 mmol) of potassium-t-butoxide was added thereto, and then the suspension was stirred while being maintained at a temperature lower than −50° C. for 2 hours to prepare a ylide. Then, 15 ml of solution of 4.7 g (10.4 mmol) of the cyclohexanecarbaldehyde derivative (40) obtained by the procedures described above in THF was added dropwise thereto at the same temperature in 5 min, stirred for 1 hour at the same temperature, warmed up to room temperature, and further stirred for 8 hours. Water in an amount of 50 ml was added to the reaction solution to terminate the reaction, the THF layer was separated, and the water layer was extracted with 50 ml of toluene. The THF layer and the toluene layer were coalesced, washed with 80 ml of water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and 6.4 g of the product thus obtained was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 1.5 g of a colorless needle-shaped compound. This compound was the objective difluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy) (4-(trans-4-propylcyclohexyl)phenyl)methane. Data of various kind of spectrums supported the structure of the compound described above.

Mass spectrum: 452 (M⁺)

EXAMPLE 8

Preparation of (2,3-difluoro-4-ethoxyphenyl)oxy(trans-4-(trans-4-n-propylcyclohexyl)cyclohexyl)difluoromethane (Compound expressed by the general formula (1) wherein m is 1, n is 0, both rings A¹ and ring A² represent trans-1,4-cyclohexylene group, ring A⁴ represents 2,3-difluoro-1,4-phenylene group, X¹ represents single bond, X² represents —CF₂O—, R¹ represents n—C₃H₇, and Y¹ represents OC₂H₅; Compound No. 144)

(First step)

First, 10.0 g (57.5 mmol) of the 2,3-difluoro-4-ethoxyphenol obtained by the method described in the second step of Example 1, 17.4 g (68.9 mmol) of trans-4-(trans-4-propylcyclohexyl)cyclohexanecarboxylic acid, 0.2 g (1.8 mmol) of DMAP, and 300 ml of dichloromethane were mixed. To this mixture was added dropwise 80 ml of solution of 12.3 g (60.0 mmol) of DCC in dichloromethane under a condition cooled with ice in 10 min, warmed up to room temperature, and then stirred as it was overnight. Separated crystals were removed by filtration, the solvent was distilled of under a reduced pressure from the filtrate, and the residue thus obtained was purified by silica gel column chromatography (eluent: toluene) and further recrystallized from heptane to obtain 20.8 g of 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-propylcyclohexyl)benzoate.

(Second step)

In a 300 ml sealed glass tube, 20.8 g (50.9 mmol) of the 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-propylcyclohexyl)benzoate was dissolved in 150 ml of toluene, 24.7 g (61.1 mmol) of Lawesson's reagent was added thereto, and then the solution was heated at 140° C. on an oil bath for 8 hours. Water in an amount of 200 ml was added to the reaction solution and then the toluene layer was separated. The toluene layer was washed with 150 ml of water thrice and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the brown residue thus obtained was purified by silica gel column chromatography (eluent: mixed solvent of heptane/toluene) and then recrystallized from heptane to obtain -6.7 g of yellow needle-shaped crystalline 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-n-propylcyclohexyl)cyclohexane-thiocarboxylate.

(Third step)

To a suspension prepared by suspending 8.5 g (47.4 mmol) of N-bromosuccinimide in 50 ml of methylene chloride was added dropwise 6.9 g of hydrogen fluoride-pyridine at -78° C. in 20 min and stirred as it was for 10 min. To this reaction solution was added dropwise 40 ml of solution of 6.7 g (15.8 mmol) of 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-n-propylcyclohexyl)cyclohexane-thiocarboxylate in methylene chloride in 40 min and stirred as it was for 2 hours. The reaction solution was poured into saturated aqueous sodium carbonate solution to terminate the reaction and then the methylene chloride layer was separated. The methylene chloride layer was washed with 10% aqueous sodium bisulfite solution and water in turn, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue thus obtained was purified by silica gel column chromatography (eluent: heptane) and further recrystallized from heptane to obtain 4.4 g of the subjective compound. Data of various kind of spectrums supported the structure of the compound described above.

¹⁹F-NMR (CDCl3) δ (ppm): −79.4 (s, —CF₂O—)

Mass spectrum: 452 (M⁺)

Compounds shown below can be prepared by selecting known procedures of organic synthesis and using them in combination with reference to the procedures described in Examples described above.

m = 1, n = 0 No. R¹ A¹ X¹ A² X² A⁴ Y¹ 1 C₃H₇

CO₂

OC₂H₅ 2 C₃H₇

CO₂

OC₂H₅ 3 C₃H₇

CO₂

OC₂H₅ 4 C₃H₇

CO₂

OCH₃ 5 C₃H₇

CO₂

OC₂H₅ 6 C₃H₇

CO₂

OC₃H₇ 7 C₅H₁₁

CO₂

OC₂H₅ 8 C₅H₁₁

CO₂

OC₂H₅ 9 C₅H₁₁

CO₂

OCH₃ 10 C₅H₁₁

CO₂

OC₂H₅ 11 C₅H₁₁

CO₂

OC₃H₇ 12 C₅H₁₁

CO₂

OCH₃ 13 C₅H₁₁

CO₂

OC₂H₅ 14 C₅H₁₁

CO₂

OC₃H₇ 15 C₃H₇

CO₂

OC₂H₅ 16 C₃H₇

CO₂

OC₂H₅ 17 C₃H₇

CO₂

OC₂H₅ 18 C₃H₇

CO₂

OCH₃ 19 C₃H₇

CO₂

OC₂H₅ 20 C₃H₇

CO₂

OC₃H₇ 21 C₅H₁₁

CO₂

OC₂H₅ 22 C₅H₁₁

CO₂

OC₂H₅ 23 C₅H₁₁

CO₂

OC₂H₅ 24 C₅H₁₁

CO₂

OCH₃ 25 C₅H₁₁

CO₂

OC₂H₅ 26 C₅H₁₁

CO₂

OC₃H₇ m = n = 1 No. R¹ A¹ X¹ A² X² A³ X³ A⁴ Y¹ 27 C₃H₇

—

CO₂

—

OC₂H₅ 28 C₃H₇

—

CO₂

—

OC₂H₅ 29 C₃H₇

—

CO₂

—

OC₂H₅ 30 C₃H₇

—

CO₂

—

OC₂H₅ 31 C₃H₇

—

CO₂

—

OCH₃ 32 C₃H₇

CO₂

—

OC₂H₅ 33 C₃H₇

CO₂

—

OC₂H₅ 34 C₃H₇

CO₂

—

OC₂H₅ 35 C₃H₇

CO₂

—

OC₂H₅ 36 C₃H₇

CO₂

—

OC₂H₅ 37 C₃H₇

CO₂

—

OC₂H₅ 38 C₃H₇

CO₂

—

OC₂H₅ 39 C₃H₇

CO₂

—

OC₂H₅ 40 C₃H₇

CO₂

—

OC₂H₅ 41 C₅H₁₁

CO₂

—

OC₃H₇ 42 C₃H₇

—

—

CO₂

OC₂H₅ 43 C₃H₇

—

—

CO₂

OCH₃ 44 C₅H₁₁

—

—

CO₂

OC₂H₅ 45 C₅H₁₁

—

—

CO₂

OC₃H₇ 46 C₃H₇

—

CO₂

OC₂H₅ 47 C₃H₇

—

CO₂

OCH₃ 48 C₅H₁₁

—

CO₂

OC₂H₅ 49 C₅H₁₁

—

CO₂

OC₃H₇ 50 C₃H₇

—

CO₂

OC₂H₅ 51 C₃H₇

—

CO₂

OCH₃ 52 C₅H₁₁

—

CO₂

OC₂H₅ 53 C₅H₁₁

—

CO₂

OC₃H₇ 54 C₃H₇

—

—

CO₂

OC₂H₅ 55 C₃H₇

—

—

CO₂

OCH₃ 56 C₅H₁₁

—

—

CO₂

OC₂H₅ 57 C₅H₁₁

—

—

CO₂

OC₃H₇ 58 C₃H₇

—

CO₂

OC₂H₅ 59 C₃H₇

—

CO₂

OCH₃ 60 C₅H₁₁

—

CO₂

OC₂H₅ 61 C₅H₁₁

—

CO₂

OC₃H₇ 62 C₃H₇

—

CO₂

OC₂H₅ 63 C₃H₇

—

CO₂

OCH₃ 64 C₅H₁₁

—

CO₂

OC₂H₅ 65 C₅H₁₁

—

CO₂

OC₃H₇ 66 C₃H₇

—

CO₂

OC₂H₅ 67 C₃H₇

—

CO₂

OCH₃ 68 C₅H₁₁

—

CO₂

OC₂H₅ 69 C₅H₁₁

—

CO₂

OC₃H₇ 70 C₃H₇

CO₂

OC₂H₅ 71 C₃H₇

CO₂

OCH₃ 72 C₅H₁₁

CO₂

OC₂H₅ 73 C₅H₁₁

CO₂

OC₃H₇ 74 C₃H₇

CO₂

OC₂H₅ 75 C₃H₇

CO₂

OCH₃ 76 C₅H₁₁

CO₂

OC₂H₅ 77 C₅H₁₁

CO₂

OC₃H₇ 78 C₃H₇

—

CO₂

OC₂H₅ 79 C₃H₇

—

CO₂

OCH₃ 80 C₅H₁₁

—

CO₂

OC₂H₅ 81 C₅H₁₁

—

CO₂

OC₃H₇ 82 C₃H₇

CO₂

OC₂H₅ 83 C₃H₇

CO₂

OCH₃ 84 C₅H₁₁

CO₂

OC₂H₅ 85 C₅H₁₁

CO₂

OC₃H₇ 86 C₃H₇

CO₂

OC₂H₅ 87 C₃H₇

CO₂

OCH₃ 88 C₅H₁₁

CO₂

OC₂H₅ 89 C₅H₁₁

CO₂

OC₃H₇ 90 C₃H₇

—

CO₂

OC₂H₅ 91 C₃H₇

—

CO₂

OC₂H₅ 92 C₃H₇

CO₂

OC₂H₅ 93 C₃H₇

CO₂

OC₂H₅ 94 C₃H₇

CO₂

OC₂H₅ 95 C₃H₇

CO₂

OC₂H₅ 96 C₅H₁₁

CO₂

OCH₃ 97 C₃H₇

—

CO₂

OC₂H₅ 98 C₃H₇

—

CO₂

OC₂H₅ 99 C₃H₇

CO₂

OC₂H₅ 100 C₃H₇

CO₂

OC₂H₅ 101 C₃H₇

CO₂

OC₂H₅ 102 C₃H₇

CO₂

OC₂H₅ 103 C₅H₁₁

CO₂

OC₃H₇ 104 C₃H₇

—

CO₂

OC₂H₅ 105 C₃H₇

—

CO₂

OC₂H₅ 106 C₃H₇

CO₂

OC₂H₅ 107 C₃H₇

CO₂

OC₂H₅ 108 C₃H₇

CO₂

OC₂H₅ 109 C₃H₇

CO₂

OC₂H₅ 110 C₅H₁₁

CO₂

OCH₃ 111 C₃H₇

—

CO₂

OC₂H₅ 112 C₃H₇

—

CO₂

OC₂H₅ 113 C₃H₇

CO₂

OC₂H₅ 114 C₃H₇

CO₂

OC₂H₅ 115 C₃H₇

CO₂

OC₂H₅ 116 C₃H₇

CO₂

OC₂H₅ 117 C₅H₁₁

CO₂

OC₃H₇ 118 C₃H₇

—

CO₂

OC₂H₅ 119 C₃H₇

—

CO₂

OC₂H₅ 120 C₃H₇

CO₂

OC₂H₅ 121 C₃H₇

CO₂

OC₂H₅ 122 C₃H₇

CO₂

OC₂H₅ 123 C₃H₇

CO₂

OC₂H₅ 124 C₅H₁₁

CO₂

OCH₃ 125 C₃H₇

—

CO₂

OC₂H₅ 126 C₃H₇

—

CO₂

OC₂H₅ 127 C₃H₇

CO₂

OC₂H₅ 128 C₃H₇

CO₂

OC₂H₅ 129 C₃H₇

CO₂

OC₂H₅ 130 C₃H₇

CO₂

OC₂H₅ 131 C₅H₁₁

CO₂

OC₃H₇ m = 1, n = 0 No. R¹ A¹ X¹ A² X² A⁴ Y¹ 132 C₃H₇

CF₂O

OC₂H₅ 133 C₃H₇

CF₂O

OC₂H₅ 134 C₃H₇

CF₂O

OC₂H₅ 135 C₃H₇

CF₂O

OCH₃ 136 C₃H₇

CF₂O

OC₂H₅ 137 C₃H₇

CF₂O

OC₃H₇ 138 C₅H₁₁

CF₂O

OC₂H₅ 139 C₅H₁₁

CF₂O

OC₂H₅ 140 C₅H₁₁

CF₂O

OC₂H₅ 141 C₅H₁₁

CF₂O

OCH₃ 142 C₅H₁₁

CF₂O

OC₂H₅ 143 C₅H₁₁

CF₂O

OC₃H₇ 144 C₃H₇

—

CF₂O

OC₂H₅ 145 C₃H₇

—

CF₂O

OC₂H₅ 146 C₃H₇

—

CF₂O

OC₂H₅ 147 C₃H₇

—

CF₂O

OCH₃ 148 C₃H₇

—

CF₂O

OC₂H₅ 149 C₃H₇

—

CF₂O

OC₃H₇ 150 C₅H₁₁

—

CF₂O

OC₂H₅ 151 C₅H₁₁

—

CF₂O

OC₂H₅ 152 C₅H₁₁

—

CF₂O

OC₂H₅ 153 C₅H₁₁

—

CF₂O

OCH₃ 154 C₅H₁₁

—

CF₂O

OC₂H₅ 155 C₅H₁₁

—

CF₂O

OC₃H₇ 156 C₃H₇

CF₂O

OC₂H₅ 157 C₃H₇

CF₂O

OC₂H₅ 158 C₃H₇

CF₂O

OC₂H₅ 159 C₃H₇

CF₂O

OCH₃ 160 C₃H₇

CF₂O

OC₂H₅ 161 C₃H₇

CF₂O

OC₃H₇ 162 C₅H₁₁

CF₂O

OC₂H₅ 163 C₅H₁₁

CF₂O

OC₂H₅ 164 C₅H₁₁

CF₂O

OC₂H₅ 165 C₅H₁₁

CF₂O

OC₂H₅ 166 C₅H₁₁

CF₂O

OC₂H₅ 167 C₅H₁₁

CF₂O

OC₂H₅ m = n = 1 No. R¹ A¹ X¹ A² X² A³ X³ A⁴ Y¹ 168 C₃H₇

—

CF₂O

—

OC₂H₅ 169 C₃H₇

—

CF₂O

—

OC₂H₅ 170 C₃H₇

—

CF₂O

—

OC₂H₅ 171 C₃H₇

—

CF₂O

—

OC₂H₅ 172 C₅H₁₁

—

CF₂O

—

OCH₃ 173 C₃H₇

CF₂O

—

OC₂H₅ 174 C₃H₇

CF₂O

—

OC₂H₅ 175 C₃H₇

CF₂O

—

OC₂H₅ 176 C₃H₇

CF₂O

—

OC₂H₅ 177 C₅H₁₁

CF₂O

—

OCH₃ 178 C₃H₇

CF₂O

—

OC₂H₅ 179 C₃H₇

CF₂O

—

OC₂H₅ 180 C₃H₇

CF₂O

—

OC₂H₅ 181 C₃H₇

CF₂O

—

OC₂H₅ 182 C₅H₁₁

CF₂O

—

OC₂H₅ 183 C₃H₇

—

CF₂O

OC₂H₅ 184 C₃H₇

—

CF₂O

OC₂H₅ 185 C₃H₇

—

CF₂O

OC₂H₅ 186 C₃H₇

—

CF₂O

OC₂H₂ 187 C₃H₇

—

CF₂O

OCH₃ 188 C₃H₇

CF₂O

OC₂H₅ 189 C₃H₇

CF₂O

OC₂H₅ 190 C₃H₇

CF₂O

OC₂H₅ 191 C₃H₇

CF₂O

OC₂H₅ 192 C₅H₁₁

CF₂O

OCH₃ 193 C₃H₇

CF₂O

OC₂H₅ 194 C₃H₇

CF₂O

OC₂H₅ 195 C₃H₇

CF₂O

OC₂H₅ 196 C₃H₇

CF₂O

OC₂H₅ 197 C₅H₁₁

CF₂O

OC₃H₇ 198 C₃H₇

—

CF₂O

—

OC₂H₅ 199 C₃H₇

—

CF₂O

—

OC₂H₅ 200 C₃H₇

—

CF₂O

—

OC₂H₅ 201 C₃H₇

—

CF₂O

—

OC₂H₅ 202 C₃H₇

—

CF₂O

—

OC₂H₅ 203 C₃H₇

CF₂O

—

OC₂H₅ 204 C₃H₇

CF₂O

—

OC₂H₅ 205 C₃H₇

CF₂O

—

OC₂H₅ 206 C₃H₇

CF₂O

—

OC₂H₅ 207 C₅H₁₁

CF₂O

—

OC₃H₇ 208 C₃H₇

CF₂O

—

OC₂H₅ 209 C₃H₇

CF₂O

—

OC₂H₅ 210 C₃H₇

CF₂O

—

OC₂H₅ 211 C₃H₇

CF₂O

—

OC₂H₅ 212 C₅H₁₁

CF₂O

—

OC₃H₇ 213 C₃H₇

—

—

CF₂O

OC₂H₅ 214 C₃H₇

—

—

CF₂O

OC₂H₅ 215 C₃H₇

—

CF₂O

OC₂H₅ 216 C₃H₇

—

CF₂O

OC₂H₅ 217 C₃H₇

—

CF₂O

OC₂H₅ 218 C₃H₇

—

CF₂O

OC₂H₅ 219 C₃H₇

—

—

CF₂O

OC₂H₅ 220 C₃H₇

—

—

CF₂O

OC₂H₅ 221 C₃H₇

—

CF₂O

OC₂H₅ 222 C₃H₇

—

CF₂O

OC₂H₅ 223 C₃H₇

—

CF₂O

OCH₃ 224 C₅H₁₁

—

CF₂O

OCH₃ 225 C₅H₁₁

—

CF₂O

OC₂H₅ 226 C₅H₁₁

—

CF₂O

OC₃H₇ 227 C₃H₇

—

—

CF₂O

OC₂H₅ 228 C₃H₇

—

—

CF₂O

OC₂H₅ 229 C₃H₇

—

CF₂O

OC₂H₅ 230 C₃H₇

—

CF₂O

OC₂H₅ 231 C₃H₇

—

CF₂O

OC₂H₅ 232 C₃H₇

—

CF₂O

OC₂H₅ 233 C₃H₇

—

—

CF₂O

OC₂H₅ 234 C₃H₇

—

—

CF₂O

OC₂H₅ 235 C₃H₇

—

CF₂O

OC₂H₅ 236 C₃H₇

—

CF₂O

OC₂H₅ 237 C₃H₇

—

CF₂O

OC₂H₅ 238 C₅H₁₁

—

CF₂O

OCH₃ 239 C₅H₁₁

—

CF₂O

OC₂H₅ 240 C₅H₁₁

—

CF₂O

OC₃H₇ 241 C₃H₇

—

CF₂O

OC₂H₅ 242 C₃H₇

—

CF₂O

OC₂H₅ 243 C₃H₇

CF₂O

OC₂H₅ 244 C₃H₇

CF₂O

OC₂H₅ 245 C₃H₇

CF₂O

OC₂H₅ 246 C₃H₇

CF₂O

OC₂H₅ 247 C₃H₇

—

CF₂O

OC₂H₅ 248 C₃H₇

—

CF₂O

OC₂H₅ 249 C₃H₇

CF₂O

OC₂H₅ 250 C₃H₇

CF₂O

OC₂H₅ 251 C₃H₇

CF₂O

OC₂H₅ 252 C₅H₁₁

CF₂O

OCH₃ 253 C₅H₁₁

CF₂O

OC₂H₅ 254 C₅H₁₁

CF₂O

OC₃H₇ 255 C₃H₇

—

CF₂O

OC₂H₅ 256 C₃H₇

—

CF₂O

OC₂H₅ 257 C₃H₇

CF₂O

OC₂H₅ 258 C₃H₇

CF₂O

OC₂H₅ 259 C₃H₇

CF₂O

OC₂H₅ 260 C₃H₇

CF₂O

OC₂H₅ 261 C₃H₇

—

CF₂O

OC₂H₅ 262 C₃H₇

—

CF₂O

OC₂H₅ 263 C₃H₇

CF₂O

OC₂H₅ 264 C₃H₇

CF₂O

OC₂H₅ 265 C₃H₇

CF₂O

OC₂H₅ 266 C₅H₁₁

CF₂O

OCH₃ 267 C₅H₁₁

CF₂O

OC₂H₅ 268 C₅H₁₁

CF₂O

OC₃H₇ 269 C₃H₇

—

CF₂O

OC₂H₅ 270 C₃H₇

—

CF₂O

OC₂H₅ 271 C₃H₇

CF₂O

OC₂H₅ 272 C₃H₇

CF₂O

OC₂H₅ 273 C₃H₇

CF₂O

OC₂H₅ 274 C₃H₇

CF₂O

OC₂H₅ 275 C₃H₇

—

CF₂O

OC₂H₅ 276 C₃H₇

—

CF₂O

OC₂H₅ 277 C₃H₇

CF₂O

OC₂H₅ 278 C₃H₇

CF₂O

OC₂H₅ 279 C₃H₇

CF₂O

OC₂H₅ 280 C₅H₁₁

CF₂O

OCH₃ 281 C₅H₁₁

CF₂O

OC₂H₅ 282 C₅H₁₁

CF₂O

OC₃H₇ 283 C₃H₇

—

CF₂O

OC₂H₅ 284 C₃H₇

—

CF₂O

OC₂H₅ 285 C₃H₇

CF₂O

OC₂H₅ 286 C₃H₇

CF₂O

OC₂H₅ 287 C₃H₇

CF₂O

OC₂H₅ 288 C₃H₇

CF₂O

OC₂H₅ 289 C₃H₇

—

CF₂O

OC₂H₅ 290 C₃H₇

—

CF₂O

OC₂H₅ 291 C₃H₇

CF₂O

OC₂H₅ 292 C₃H₇

CF₂O

OC₂H₅ 293 C₃H₇

CF₂O

OC₂H₅ 294 C₅H₁₁

CF₂O

OCH₃ 295 C₅H₁₁

CF₂O

OC₂H₅ 296 C₅H₁₁

CF₂O

OC₃H₇ m = n = 0 No. R¹ A¹ X¹ A⁴ Y¹ 297 C₃H₇

COO

OCH₃ 298 C₃H₇

COO

OC₂H₅ 299 C₃H₇

COO

OC₃H₇ 300 C₅H₁₁

COO

OCH₃ 301 C₅H₁₁

COO

OC₂H₅ 302 C₅H₁₁

COO

OC₃H₇ 303 C₃H₇

CF₂O

OC₂H₅ 304 C₃H₇

CF₂O

OCH₃ 305 C₃H₇

CF₂O

OC₂H₅ 306 C₃H₇

CF₂O

OC₃H₇ 307 C₅H₁₁

CF₂O

OC₂H₅ 308 C₅H₁₁

CF₂O

OCH₃ 309 C₅H₁₁

CF₂O

OC₂H₅ 310 C₅H₁₁

CF₂O

OC₃H₇ No.

311

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312

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313

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314

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315

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329

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398

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469

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572

S_(A) 106.3 N 170.0 Iso 573

574

575

Cr 57.9-58.4 N 198.9-199.4 Iso 576

S_(B) 75.5-76.5 N 191.9-192.5 Iso 577

578

579

580

581

582

583

584

585

586

587

588

589

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591

S_(B) 120.8 N 198.6 Iso 592

Cr 117.7 S_(B) 120.5 N 193.9 Iso 593

594

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USE EXAMPLES

In the Use Examples shown below, value of dielectric anisotropy Δε was determined by using a TN cell (twisted nematic cell) having a cell thickness of 9 μm at 25° C.

EXAMPLE 9 Use Example 1

Clearing point (Cp) of a nematic liquid crystal of liquid crystal composition (hereinafter referred to as mother liquid crystal A) comprising the following compounds each in the amount shown below

4-butoxyphenyl 4-(trans-4-propylcyclohexyl)carboxybenzoate

27.6% (by weight, the same unit is applied below)

4-ethoxyphenyl 4-(trans-4-butylcyclohexyl)carboxybenzoate

20.7%

4-methoxyphenyl 4-(trans-4-pentylcyclohexyl)carboxybenzoate

20.7%

4-ethoxyphenyl 4-(trans-4-propylcyclohexyl)carboxybenzoate

17.2%

4-ethoxyphenyl 4-(trans-4-pentylcyclohexyl)carboxybenzoate

13.8%

was 74.6° C. and its Δε was 0.0.

This mother liquid crystal A in an amount of 85 parts by weight was mixed with 15 parts by weight of the 2,3-difluoro-4-ethoxyphenyl 2-fluoro-4-(2-(trans-4-propylcyclohexyl)ethyl)benzoate (Compound No. 15) obtained in Example 1, and its physical properties were determined. Value of the physical properties of the compound obtained by extrapolation from the results were as follows:

Cp: 129.4° C., Δε: −4.17

EXAMPLE 10 Use Example 2

Mother liquid crystal A in an amount of 90 parts by weight was mixed with 10 parts by weight of 2,3-difluoro-4-ethoxyphenyl 4-(2-(trans-4-pentylcyclohexyl)vinyl)cyclohexyl-carboxylate (Compound No. 7), and its physical properties were determined. Value of the physical properties of the compound obtained by extrapolation from the results were as follows:

Cp: 187.1° C., Δε: −5.67

EXAMPLE 11 Use Example 3

Mother liquid crystal A in an amount of 85 parts by weight was mixed with 15 parts by weight of the (2,3-difluoro-4ethoxyphenyl)oxy(4-(trans-4-n-pentylcyclohexyl)phenyl)difluoromethane (Compound No. 152) obtained in Example 2, and its physical properties were determined. Value of the physical properties of the compound obtained by extrapolation from the results were as follows:

Cp: 114.1IC, Δε: −4.20

EXAMPLE 12 Use Example 4

Clearing point (Cp) of a nematic liquid crystal of liquid crystal composition (hereinafter referred to as mother liquid crystal B) comprising the following compounds each in the amount shown below

4-(trans-4-propylcyclohexyl)benzonitrile 24% (by weight, the same unit is applied below)

4-(trans-4-pentylcyclohexyl)benzonitrile 36%

4-(trans-4-heptylcyclohexyl)benzonitrile 25%

4-(4-propylphenyl)benzonitrile 15%

was 72.4° C. When this liquid crystal composition was filled in a TN cell (twisted nematic cell) having a cell thickness of 9 μm, its driving threshold voltage (Vth) was 1.78 V, value of dielectric anisotropy (Δε) was +11.0, value of optical anisotropy (Δn) was 0.137, and viscosity at 20° C. (η₂₀) was 27.0 mPa·s.

This mother liquid crystal B in an amount of 85 parts by weight was mixed with 15 parts by weight of the difluoro-(4-(trans-4-propylcyclohexyl)phenyloxy) (4-(trans-4-pentylcyclohexyl)phenyl)methane (Compound No. 572) obtained in Example 6, and its physical properties were determined. The results were as follows:

Cp: 90.3° C., Vth: 1.81 V, Δε: 9.9, Δn: 0.136, η₂₀: 28.4 mPa·s

Further, while this liquid crystal composition was left in a freezer at −20° C. for 25 days, separation of crystals or development of smectic phase was not noticed.

EXAMPLE 13 Use Example 5

Mother liquid crystal B in an amount of 85 parts by weight was mixed with 15 parts by weight of difluoro-(4-(trans-4-propylcyclohexyl)phenyloxy) (4-(2-(trans-4-propylcyclohexyl)ethyl)phenyl)methane (Compound No. 591), and its physical properties were determined. The results were as follows:

Cp: 87.2° C., Vth: 1.85 V, Δε: 9.9, Δn: 0.137, η₂₀: 28.2 mPa·s

Further, while this liquid crystal composition was left in a freezer at −20° C. for 25 days, separation of crystals or development of smectic phase was not noticed.

EXAMPLE 14 Use Example 6

Mother liquid crystal B in an amount of 85 parts by weight was mixed with 15 parts by weight of difluoro-(4-(trans-4-pentylcyclohexyl)phenyloxy) (4-(2-(trans-4-propylcyclohexyl)ethyl)phenyl)methane (Compound No. 592), and its physical properties were determined. The results were as follows:

Cp: 89.8° C., Vth: 1.87 V, Δε: 9.7, Δn: 0.136, η₂₀: 29.0 mPa·s

Further, while this liquid crystal composition was left in a freezer at −20° C. for 25 days, separation of crystals or development of smectic phase was not noticed.

EXAMPLE 15 Use Example 7

Physical properties of the liquid crystal composition shown in Composition Example 1 were determined. As the results, Cp was 90.2 and Δε was 6.8.

EXAMPLE 16 Use Example 8

Physical properties of the liquid crystal composition shown in Composition Example 2 were determined. As the results, Cp was 87.1 and Δε was 8.5.

EXAMPLE 17 Use Example 9

Physical properties of the liquid crystal composition shown in Composition Example 3 were determined. As the results, Cp was 94.0 and Δε was 29.8.

EXAMPLE 18 Use Example 10

Physical properties of the liquid crystal composition shown in Composition Example 4 were determined. As the results, Cp was 91.7 and Δε was 6.1.

EXAMPLE 19 Use Example 11

Physical properties of the liquid crystal composition shown in Composition Example 5 were determined. As the results, Cp was 79.4 and Δε was 7.2.

EXAMPLE 20 Use Example 12

Physical properties of the liquid crystal composition shown in Composition Example 6 were determined. As the results, Cp was 91.4 and Δε was 4.5.

EXAMPLE 21 Use Example 13

Physical properties of the liquid crystal composition shown in Composition Example 7 were determined. As the results, Cp was 87.1 and Δε was 27.9.

EXAMPLE 22 Use Example 14

Physical properties of the liquid crystal composition shown in Composition Example 8 were determined. As the results, Cp was 62.1 and Δε was 9.6.

EXAMPLE 23 Use Example 15

Physical properties of the liquid crystal composition shown in Composition Example 9 were determined. As the results, Cp was 64.1 and Δε was 6.0.

EXAMPLE 24 Use Example 16

Physical properties of the liquid crystal composition shown in Composition Example 10 were determined. As the results, Cp was 100.7 and Δε was 7.5.

EXAMPLE 25 Use Example 17

Physical properties of the liquid crystal composition shown in Composition Example 11 were determined. As the results, Cp was 96.6 and AΔε was 6.4.

EXAMPLE 26 Use Example 18

Physical properties of the liquid crystal composition shown in Composition Example 12 were determined. As the results, Cp was 79.8 and Δε was 6.2.

EXAMPLE 27 Use Example 19

Physical properties of the liquid crystal composition shown in Composition Example 13 were determined. As the results, Cp was 94.5 and Δε was 3.8.

EXAMPLE 28 Use Example 20

Physical properties of the liquid crystal composition shown in Composition Example 14 were determined. As the results, Cp was 99.8 and Δε was 4.6.

EXAMPLE 29 Use Example 21

Physical properties of the liquid crystal composition shown in Composition Example 15 were determined. As the results, Cp was 88.5 and Δε was 2.9.

EXAMPLE 30 Use Example 22

Physical properties of the liquid crystal composition shown in Composition Example 16 were determined. As the results, Cp was 86.5 and Δε was 5.4.

EXAMPLE 31 Use Example 23

Physical properties of the liquid crystal composition shown in Composition Example 17 were determined. As the results, Cp was 73.8 and Δε was 8.4.

EXAMPLE 32 Use Example 24

Physical properties of the liquid crystal composition shown in Composition Example 18 were determined. As the results, Cp was 76.8 and Δε was 12.6.

EXAMPLE 33 Use Example 25

Physical properties of the liquid crystal composition shown in Composition Example 19 were determined. As the results, Cp was 97.0 and Δε was 8.1.

EXAMPLE 34 Use Example 26

Physical properties of the liquid crystal composition shown in Composition Example 20 were determined. As the results, Cp was 83.1 and Δε was 4.1.

EXAMPLE 35 Use Example 27

Physical properties of the liquid crystal composition shown in Composition Example 21 were determined. AS the results, Cp was 82.4 and AΔε was −1.8.

EXAMPLE 36 Use Example 28

Physical properties of the liquid crystal composition shown in Composition Example 22 were determined. As the results, Cp was 77.3 and Δε was −2.1.

EXAMPLE 37 Use Example 29

Physical properties of the liquid crystal composition shown in Composition Example 23 were determined. As the results, Cp was 78.8 and Δε was −3.0.

In addition to the Examples shown above, the following Examples (Use Examples) can be shown. In the following Examples, compounds are designated by using symbols according to the definitions shown in Table 1 described above, and T_(NI) indicates clearing point, η: viscosity, Δn: optical anisotropy value, Δε: dielectric anisotropy value, V_(th): threshold voltage, and P: pitch.

EXAMPLE 38 Use Example 30

5-HBCF2OBH-3 3.0% 2-HB(F)OCF2BH 3.0% 1V2-BEB(F,F)—C 5.0% 3-HB—C 25.0% 1-BTB-3 5.0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 5.0% 3-HHB-3 9.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0% T_(NI) = 92.4 (° C.) η = 16.0 (mPa.s) Δn = 0.162 Δε = 7.0 V_(th) = 2.12 (V)

Pitch of a liquid crystal composition prepared by adding 0.8 part by weight of optically active compound CM 33 to 100 parts by weight of the liquid crystal composition described above was as follows:

P=11 μm

EXAMPLE 39 Use Example 31

3-H2BCF2OBH-5 5.0% 3-HB(F,F)OCF2BH-5 5.0% 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 15.0% 4O1-BEB(F)—C 13.0% 5O1-BEB(F)—C 13.0% 2-HHB(F)—C 15.0% 3-HHB(F)—C 5.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 8.0% 3-HHB—O1 4.0% T_(NI) = 92.9 (° C.) η = 86.0 (mPa.s) Δn = 0.146 Δε = 29.7 V_(th) = 0.90 (V)

EXAMPLE 40 Use Example 32

3-H2BCF2OBH-5 4.0% 3-HB(F,F)OCF2BH-5 4.0% 2-BEB—C 12.0% 3-BEB—C 4.0% 4-BEB—C 6.0% 3-HB—C 28.0% 3-HEB—O4 12.0% 4-HEB—O2 8.0% 5-HEB—O1 4.0% 3-HEB—O2 6.0% 5-HEB—O2 5.0% 3-HHB-1 3.0% 3-HHB—O1 4.0% T_(NI) = 67.8 (° C.) η = 28.2 (mPa.s) Δn = 0.115 Δε = 10.0 V_(th) = 1.35 (V)

EXAMPLE 41 Use Example 33

5-HBCF2OBH-3 3.0% 3-H2BCF2OBH-3 3.0% 7-HB(F)—F 5.0% 5-H2B(F)—F 5.0% 3-HB—O2 10.0% 3-HH-4 5.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 3-H2HB(F)—F 5.0% 2-HBB(F)—F 3.0% 3-HBB(F)—F 3.0% 5-HBB(F)—F 6.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 6.0% 3-HHB-1 2.0% 3-HHB—O1 5.0% 3-HHB-3 4.0% T_(NI) = 90.6 (° C.) η = 19.4 (mPa.s) Δn = 0.093 Δε = 3.2 V_(th) = 2.67 (V)

EXAMPLE 42 Use Example 34

3-H2BCF2OBH-3 4.0% 2-HB(F)OCF2BH-5 3.0% 5-HVHEB(2F,3F)—O2 3.0% 7-HB(F,F)—F 3.0% 3-HB—O2 7.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 2-HBB(F)—F 9.0% 3-HBB(F)—F 9.0% 5-HBB(F)—F 6.0% 2-HBB—F 4.0% 3-HBB—F 4.0% 5-HBB—F 3.0% 3-HBB(F,F)—F 5.0% 5-HBB(F,F)—F 10.0% T_(NI) = 93.0 (° C.) η = 24.1 (mPa.s) Δn = 0.113 Δε = 5.8 V_(th) = 1.99 (V)

EXAMPLE 43 Use Example 35

5-HBCF2OBH-3 3.0% 3-H2BCF2OBH-5 3.0% 3-HB(F,F)OCF2BH-5 3.0% 7-HB(F,F)—F 4.0% 3-H2HB(F,F)—F 12.0% 4-H2HB(F,F)—F 10.0% 5-H2HB(F,F)—F 10.0% 3-HHB(F,F)—F 10.0% 4-HHB(F,F)—F 5.0% 3-HH2B(F,F)—F 10.0% 5-HH2B(F,F)—F 6.0% 3-HBB(F,F)—F 12.0% 5-HBB(F,F)—F 12.0% T_(NI) = 81.4 (° C.) η = 28.8 (mPa.s) Δn = 0.079 Δε = 8.2 V_(th) = 1.61 (V)

EXAMPLE 44 Use Example 36

2-HB(F)OCF2BH-5 4.0% 3-HB(F,F)OCF2BH-5 4.0% 3-HB—CL 10.0% 5-HB—CL 4.0% 7-HB—CL 4.0% 1O1-HH-5 5.0% 2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0% 5-HBB(F)—F 14.0% 4-HHB—CL 8.0% 3-H2HB(F)—CL 4.0% 3-HBB(F,F)—F 10.0% 5-H2BB(F,F)—F 9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0% T_(NI) = 90.5 (° C.) η = 22.9 (mPa.s) Δn = 0.128 Δε = 4.7 V_(th) = 2.37 (V)

EXAMPLE 45 Use Example 37

5-HBCF2OB(2F,3F)—O2 15.0% 3-HEB—O4 24.0% 4-HEB—O2 17.0% 5-HEB—O1 17.0% 3-HEB—O2 15.0% 5-HEB—O2 12.0% T_(NI) = 80.1 (° C.) η = 23.2 (mPa.s) Δn = 0.092 Δε = −1.8

EXAMPLE 46 Use Example 38

3-H2B(F)EB(2F,3F)—O2 15.0% 3-HEB—O4 24.0% 4-HEB—O2 17.0% 5-HEB—O1 17.0% 3-HEB—O2 15.0% 5-HEB—O2 12.0% T_(NI) = 82.4 (° C.) η = 29.1 (mPa.s) Δn = 0.093

EXAMPLE 47 Use Example 39

3-H2B(F)EB(2F,3F)—O2 5.0% 5-HVHEB(2F,3F)—O2 5.0% 3-HH-2 5.0% 3-HH-4 6.0% 3-HH—O1 4.0% 3-HH—O3 5.0% 5-HH—O1 4.0% 3-HB(2F,3F)—O2 12.0% 5-HB(2F,3F)—O2 11.0% 3-HHB(2F,3F)—O2 4.0% 5-HHB(2F,3F)—O2 15.0% 3-HHB(2F,3F)-2 24.0% T_(NI) = 84.6 (° C.) Δn = 0.083 Δε = −3.9

EXAMPLE 48 Use Example 40

5-HVHEB(2F,3F)—O2 5.0% 3-HH-5 5.0% 3-HH-4 5.0% 3-HH—O1 6.0% 3-HH—O3 6.0% 3-HB—O1 5.0% 3-HB—O2 5.0% 3-HB(2F,3F)—O2 10.0% 5-HB(2F,3F)—O2 10.0% 3-HHB(2F,3F)—O2 12.0% 5-HHB(2F,3F)—O2 8.0% 3-HHB(2F,3F)-2 4.0% 2-HHB(2F,3F)-1 4.0% 3-HHEH-3 5.0% 3-HHEH-5 5.0% 4-HHEH-3 5.0% T_(NI) = 85.5 (° C.) Δn = 0.079 Δε = −3.4

EXAMPLE 49 Use Example 41

3-h2B(F)EB(2F,3F)—O2 5.0% 5-HBCF2OB(2F,3F)—O2 5.0% 3-BB(2F,3F)—O2 12.0% 3-BB(2F,3F)—O4 10.0% 5-BB(2F,3F)—O4 10.0% 2-BB(2F,3F)B-3 25.0% 3-BB(2F,3F)B-5 13.0% 5-BB(2F,3F)B-5 14.0% 5-BB(2F,3F)B-7 6.0% T_(NI) = 72.5 (° C.) Δn = 0.188 Δε = −3.6

EXAMPLE 50 Use Example 42

5-HBCF2OBH-3 3.0% 3-H2B(F)EB(2F,3F)—O2 4.0% 5-HVHEB(2F,3F)—O2 4.0% 5-HBCF2OB(2F,3F)—O2 4.0% 3-BB(2F,3F)—O2 10.0% 5-BB-5 9.0% 5-BB—O6 9.0% 5-BB—O8 8.0% 1-BEB-5 6.0 & 3-BEB-5 6.0 & 5-BEB-5 3.0 & 3-HEB—O2 20.0% 5-BBB(2F,3F)-7 9.0% 3-H2BB(2F)-5 5.0% T_(NI) = 79.1 (° C.) Δn = 0.145 Δε = −3.1

EXAMPLE 51 Use Example 43

3-H2BCF2OBH-5 3.0% 3-H2B(F)EB(2F,3F)—O2 9.0% 5-HVHEB(2F,3F)—O2 9.0% 5-HBCF2OB(2F,3F)—O2 9.0% 3-HB—O1 15.0% 3-HB—O2 6.0% 3-HEB(2F,3F)—O2 9.0% 4-HEB(2F,3F)—O2 9.0% 5-HEB(2F,3F)—O2 4.0% 2-BB2B—O2 6.0% 1-B2BB(2F)-5 7.0% 5-B(3F)BB—O2 7.0% 3-BB(2F,3F)B-3 7.0% T_(NI) = 84.5 (° C.) Δn = 0.145 η = 32.0 (mPa.s)

EXAMPLE 52 Use Example 44

5-HVHEB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 3.0% 3-HB—O1 9.0% 3-HB—O2 9.0% 3-HB—O4 9.0% 2-BTB—O1 5.0% 1-BTB—O2 5.0% 3-BTB(2F,3F)—O2 13.0% 5-BTB(2F,3F)—O2 13.0% 3-B(2F,3F)TB(2F,3F)—O4 4.0% 5-B(2F,3F)TB(2F,3F)—O4 4.0% 3-HBTB—O1 5.0% 3-HBTB—O3 5.0% 3-HHB(2F,3F)—O2 6.0% 5-HBB(2F,3F)—O2 4.0% 5-BPr(F)—O2 3.0% T_(NI) = 82.4 (° C.) Δn = 0.210

EXAMPLE 53 Use Example 45

3-H2B(F)EB(2F,3F)—O2 5.0% 5-HBCF2OB(2F,3F)—O2 5.0% 3-HB—O2 10.0% 5-HB-3 8.0% 5-BB(2F,3F)—O2 10.0% 3-HB(2F,3F)—O2 10.0% 5-HB(2F,3F)—O2 8.0% 3-HHB(2F,3F)—O2 7.0% 5-HHB(2F,3F)—O2 4.0% 5-HHB(2F,3F)-1O1 4.0% 2-HHB(2F,3F)-1 5.0% 3-HBB-2 6.0% 3-BB(2F,3F)B-3 8.0% 5-B2BB(2F,3F0B—O2 10.0% T_(NI) = 69.9 (° C.) Δn = 0.143 Δε = −3.9

EXAMPLE 54 Use Example 46

3-H2B(F)EB(2F,3F)—O2 3.0% 5-HVHEB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 3.0% 3-HB—O2 20.0% 1O1-HH-3 6.0% 1O1-HH-5 5.0% 3-HH—EMe 12.0% 4-HEB—O1 9.0% 4-HEB—O2 7.0% 5-HEB—O1 8.0% 3-HHB-1 3.0% 4-HEB(2CN, 3CN)—O4 3.0% 6-HEB(2CN, 3CN)—O4 3.0% 3-HEB(2CN, 3CN)—O5 4.0% 4-HEB(2CN, 3CN)—O5 3.0% 5-HEB(2CN, 3CN)—O5 2.0% 2-HBEB(2CN, 3CN)—O2 2.0% 4-HBEB(2CN, 3CN)—O4 4.0% T_(NI) = 63.9 (° C.) Δn = 0.073 η = 43.3 (mPa.s) Δε = −5.7

EXAMPLE 55 Use Example 47

3-H2B(F)EB(2F,3F)—O2 5.0% 1V2-BEB(F,F)—C 5.0% 3-HB—C 20.0% V2-HB—C 6.0% 1-BTB-3 5.0% 2-BTB-1 10.0% 1O1-HH-3 3.0% 3-HH-4 11.0% 3-HHB-1 11.0% 3-HHB-3 3.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HHB—C 3.0% T_(NI) = 88.1 (° C.) η = 17.9 (mPa.s) Δn = 0.156 Δε = 7.1 V_(th) = 2.09 (V)

Pitch of a liquid crystal composition prepared by adding 0.8 part by weight of optically active compound CM 33 to 100 parts by weight of the liquid crystal composition described above was as follows:

P=11.0 μm

EXAMPLE 56 Use Example 48

3-H2B(F)EB(2F,3F)—O2 5.0% 5-HVHEB(2F,3F)—O2 5.0% 5-PyB—F 4.0% 3-PyB(F)—F 4.0% 2-BB—C 5.0% 4-BB—C 4.0% 5-BB—C 5.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB—O5 3.0% 6-PyB—O6 3.0% 6-PyB—O7 3.0% 6-PyB—O8 3.0% 3-PyBB—F 6.0% 4-PyBB—F 6.0% 5-PyBB—F 6.0% 3-HHB-1 6.0% 3-HHB-3 3.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% T_(NI) = 94.3 (° C.) η 39.7 (mPa.s) Δn = 0.197 Δε = 6.6 V_(th) = 2.23 (V)

EXAMPLE 57 Use Example 49

3-H2B(F)EB(2F,3F)—O2 3.0% 5-HVHEB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 3.0% 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 12.0% 5O1-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 10.0% 3-HEB—O4 4.0% 3-HH—EMe 6.0% 3-HB—O2 18.0% 7-HEB—F 2.0% 3-HHEB—F 2.0% 5-HHEB—F 2.0% 3-HBEB—F 4.0% 2O1-HBEB(F)—C 2.0% 3-HB(F)EB(F)—C 2.0% 3-HBEB(F,F)—C 2.0% 3-HHB—F 4.0% 3-HHB—O1 4.0% 3-HEBEB—F 2.0% 3-HEBEB-1 2.0% 3-HHB(F)—C 4.0% T_(NI) = 78.3 (° C,) η = 40.6 (mPa.s) Δn = 0.116 Δε = 24.3 V_(th) = 0.95 (V)

EXAMPLE 58 Use Example 50

3-H2B(F)EB(2F,3F)—O2 3.0% 5-HBCF2OB(2F,3F)—O2 3.0% 7-HB(F)—F 5.0% 5-H2B(F)—F 5.0% 3-HB—O2 10.0% 3-HH-4 5.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 3-H2HB(F)—F 5.0% 2-HBB(F)—F 3.0% 3-HBB(F)—F 3.0% 5-HBB(F)—F 6.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 6.0% 3-HHB-1 2.0% 3-HHB—O1 5.0% 3-HHB-3 4.0% T_(NI) = 85.2 (° C.) η = 25.9 (mPa.s) Δn = 0.093 Δε = 3.4 V_(th) = 2.62 (V)

Pitch of a liquid crystal composition prepared by adding 0.3 part by weight of optically active compound CN to 100 parts by weight of the liquid crystal composition described above was as follows:

P=75 μm

EXAMPLE 59 Use Example 51

5-HVHEB(2F,3F)—O2 5.0% 3-HB—CL 10.0% 5-HB—CL 4.0% 7-HB—CL 4.0% 1O1-HH-5 5.0% 2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0% 5-HBB(F)—F 14.0% 4-HHB—CL 8.0% 5-HHB—CL 3.0% 3-H2HB(F)—CL 4.0% 3-HBB(F,F)—F 10.0% 5-H2BB(F,F)—F 9.0% 3-HB(F)—VB-2 4.0% 3-H2BTB-2 4.0% T_(NI) = 91.2 (° C.) η = 20.8 (mPa.s) Δn = 0.128 Δε = 4.8 V_(th) = 2.35 (V)

EXAMPLE 60 Use Example 52

3-H2BCF2OBH-3 2.0% 3-H2B(F)EB(2F,3F)—O2 4.0% 5-HBCF2OB(2F,3F)—O2 4.0% 5-HB—F 12.0% 6-HB—F 9.0% 7-HB—F 7.0% 2-HHB—OCF3 2.0% 3-HHB—OCF3 7.0% 4-HHB—OCF3 7.0% 3-HH2B—OCF3 4.0% 5-HH2B—OCF3 4.0% 3-HHB(F,F)—OCF3 5.0% 3-HBB(F)—F 10.0% 3-HBB(F)—F 10.0% 3-HH2B(F)—F 3.0% 3-HB(F)BH-3 3.0% 5-HBBH-3 3.0% 3-HHB(F,F)—OCF2H 4.0% T_(NI) = 87.2 (° C.) η = 18.6 (mPa.s) Δn = 0.096 Δε = 4.6 V_(th) = 2.37 (V)

EXAMPLE 61 Use Example 53

3-H2B(F)EB(2F,3F)—O2 5.0% 5-HVHEB(2F,3F)—O2 5.0% 5HBCF2OB(2F,3F)—O2 5.0% 2-HHB(F)—F 2.0% 3-HHB(F)—F 2.0% 5-HHB(F)—F 2.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 10.0% 3-H2BB(F)—F 9.0% 3-HBB(F,F)—F 25.0% 5-HBB(F,F)—F 19.0% 1O1-HBBH-4 2.0% 1O1-HBBH-5 2.0% T_(NI) = 94.7 (° C.) η = 31.6 (mPa.s) Δn = 0.131 Δε = 7.0 V_(th) = 1.95 (V)

COMPARATIVE EXAMPLES 1 AND 2

As compounds to be compared with ones of the present invention, compound (c-1) described in Japanese Patent Publication No. Sho 62-39136 (R═C₃H₇, R′═CH₃) and compound (d-1) described in Japanese patent Publication No. Sho 62-46527 (R═C₅H₁₁, R′═C₃H₇, X═Y═H) were synthesized according to a preparation method described in each of the patent publications.

Mother liquid crystal B in an amount of 85 parts by weight and 15 parts by weight of compound (c-1), and 85 parts by weight of mother liquid crystal B and 15 parts by weight of compound (d-1) were mixed, respectively, to prepare two liquid crystal compositions, and the physical properties of the liquid crystal compositions were determined. Further, liquid crystal compositions thus prepared were left in separate freezers each kept at −20° C., and miscibility was judged by counting the number of days lapsed from the day when the compositions were put in the freezer until the day when crystals separated (or smectic phase developed) in the liquid crystal compositions. These results are shown in Table 2 together with the results in Example 12 (Use Example 4) (numeral shown in the parentheses indicate the value of physical properties of each of the compounds obtained by extrapolation from the mother liquid crystal).

TABLE 2 Vth Cp (° C.) Δε η₂₀ (mPa · s) (V) Miscibil.^(*1) Mother liquid crystal B  72.4 11.0  27.5 1.78 >25 Com. Ex. 1

 85.6 (159.7) 9.6 (2.3) 26.8 (28.5) 1.96 — >25 Com. Ex. 2

100.8 (261.7) 9.5 (1.0) 31.8 (59.0) 2.02 —  15 Ex. 12

 90.3 (191.7) 9.9 (3.7) 28.4 (33.5) 1.81 — >25 ^(*1)Miscibility: Number of days lapsed from the day when the liquid crystal composition was left in a freezer at −20° C. until the day when crystals (solid such as smectic phase) separated.

In Comparative Example 1, whereas viscosity of the liquid crystal composition lowered compared with mother liquid crystal B, threshold voltage raised by 0.18 V. In Comparative Example 2, whereas it is demonstrated that comparative compound (d-1) was remarkable than compound (c-1) in the effect of raising clearing point, viscosity of liquid crystal composition was higher than mother liquid crystal B, and as to the threshold voltage, its value raised by as large as 0.24 V. In such a way, although compounds (c-1) and (d-1) have a respective merit, they have a defect that threshold voltage becomes high, and thereby it can be understood that the compounds can not be used for liquid crystal compositions for low voltage driving. In contrast to the comparative compounds, a compound of the present invention (Compound No. 572, Example 12) has an intermediate ability between compound (c-1) and compound (d-1) in the effect of raising clearing point; exhibits such a low viscosity as that of three rings compound (c-1) despite of having a four rings structure; and to our surprise, exhibits almost the same threshold voltage as mother liquid crystal B. That is, this compound can raise clearing point by nearly 20° C. by adding to mother liquid crystal B with hardly affecting threshold voltage.

Four rings compound (d-1) is very strong in smectogenecity, and development of its smectic phase was confirmed in a freezer at −20° C. in 15 days. In contrast to compound (d-1), separation of crystals was not noticed over 25 days with the compound of the present invention and the present compound was confirmed to have considerably excellent miscibility at low temperatures.

COMPARATIVE EXAMPLE 3

Mother liquid crystal B in an amount of 85 parts by weight was mixed with 15 parts by weight of compound (c-1) to prepare a liquid crystal composition and its physical properties were determined. The results are shown in Table 3 together with the results in Example 9 (Use Example 1) to Example 11 (Use Example 3).

TABLE 3 Cp (° C.) Δε Mother liquid crystal A 74.6 0.0 Com. Ex. 3

160.7 1.4 Ex. 9

129.4 −4.17 Ex. 10

187.1 −5.67 Ex. 11

114.1 −4.20

In the value of negative dielectric anisotropy which is considered to be important in IPS driving, whereas the dielectric anisotropy value obtained by extrapolation with the compound (c-1) was 1.4, the value of the compound of Examples 9, 10, and 11 exhibited remarkably as large negative value as −4.17, −5.67, and −4.20, respectively. Further, whereas the clearing point obtained by extrapolation with compound (c-1) was 160.6, that of the compound of Examples 9, 10, and 11 were such closely resembled values as 129.4° C., 187.1° C., and 114.4° C., respectively.

As described above, the liquid crystalline compounds of the present invention are very effective in largely reducing dielectric anisotropy value and have characteristics which can sufficiently cope with IPS driving.

Industrial Applicability

As will be clear from the Examples and Comparative Examples described above, the liquid crystalline compounds of the present invention are excellent in an overall balance of

1) effect of raising clearing point of liquid crystal compositions,

2) effect of lowering viscosity of liquid crystal compositions, and

3) effect of not lowering dielectric anisotropy (raising threshold voltage) of liquid crystal compositions;

have a low viscosity and negative large dielectric anisotropy; and have very useful characteristics which can not be found in known liquid crystalline compounds. 

What is claimed is:
 1. A liquid crystalline compound expressed by the general formula (1)

wherein R¹ and Y¹ represent an alkyl group having 1 to 20 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom, sulfur atom, or vinylene group; X¹, X², and X³ independently represent single bond, 1,2-ethylene group, vinylene group, —COO—, —CF₂O—, or —OCF₂— provided that at least one of X¹, X², and X³ represents —CF₂O— or —OCF₂—; ring A¹, ring A², ring A³, and ring A⁴ independently represent trans-1,4-cyclohexylene group CH₂ group on which ring may be replaced by oxygen atom, or 1,4-phenylene group one or more hydrogen atoms of which may be replaced by fluorine atom or chlorine atom; and m and n are independently 0 or 1; provided that at least one ring among A¹, ring A², ring A³, and ring A⁴ represents 1,4-phenylene group at least one hydrogen atom in which group is replaced by fluorine atom or chlorine atom; and when m=n=0, and X¹ represents —CF₂O or —OCF₂, then ring A¹ or ring A⁴ represents trans-1,4-cyclohexylene group; when m+n≧1 and at least two among X¹, X², and X³ are bonding groups selected from —CF₂O— or —OCF₂—, then at least one of rings which bond directly to the carbon atom in the —CF₂O— or —OCF₂— is trans-1,4-cyclohexylene group.
 2. The liquid crystalline compound according to claim 1 wherein m=n=0 in the general formula (1).
 3. The liquid crystalline compound according to claim 1 wherein m=1, n=0, and X¹ or X² is —CF₂O— or —OCF₂— in the general formula (1).
 4. The liquid crystalline compound according to claim 3 wherein both R¹ and Y¹ are an alkyl group in the general formula (1).
 5. The liquid crystalline compound according to claim 3 wherein at least one of R¹ and Y¹ is an alkenyl group in the general formula (1).
 6. The liquid crystalline compound according to claim 3 wherein X¹ is single bond, X² is —CF₂O— or —OCF₂—, both ring A¹ and ring A² are 1,4-cyclohexylene group, and ring A⁴ is 1,4-phenylene group at least one hydrogen atom of which is replaced by fluorine atom or chlorine atom in the general formula (1).
 7. The liquid crystalline compound according to claim 1 wherein m=n=1, and X¹, X², or X³ is -CF₂O— or OCF₂— in the general formula (1).
 8. The liquid crystalline compound according to claim 7 wherein at least one of R¹ and Y¹ is an alkenyl group in the general formula (1).
 9. The liquid crystalline compound according to claim 7 wherein R¹ and Y¹ are an alkyl group, both ring A¹ and ring A⁴ are 1,4-cyclohexylene group, any one of ring A² and ring A³ is 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom or chlorine atom and the other is 1,4-phenylene group at least one hydrogen atom of which is replaced by fluorine atom or chlorine atom, X² is —CF₂O— or —OCF₂—, and both X¹ and X³ are single bond in the general formula (1).
 10. The liquid crystalline compound according to claim 7 wherein R¹ and Y¹ are an alkyl group, both ring A¹ and ring A⁴ are 1,4-cyclohexylene group, any one of ring A² and ring A³ is 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom or chlorine atom and the other is 1,4-phenylene group at least one hydrogen atom of which is replaced by fluorine atom or chlorine atom, X² is —CF₂O— or —OCF₂—, and any one of X¹ and X³ are single bond and the other is 1,2-ethylene group in the general formula (1).
 11. A liquid crystal composition comprising at least two components at least one of which is a liquid crystalline compound expressed by the general formula (1) according to claim
 1. 12. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, and, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom; and ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom.
 13. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, and, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents CN group or —C≡C—CN; ring D represents trans-1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene, 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom, or pyrimidine-2,5-diyl group; ring F represents trans-1,4-cyclohexylene or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; and a, b, and c are independently 0 or
 1. 14. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, and, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH≡CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K represents trans-1,4-cyclohexylene or 1,4-phenylene group; and Z⁶ and Z⁷ independently represent —CH₂CH₂—, —CH₂O—, or single bond.
 15. A liquid crystal composition comprising one or more optically active compounds in addition to the liquid crystal composition defined in claim
 11. 16. A liquid crystal display device comprising the liquid crystal composition defined in claim
 11. 17. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, and as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-,1,4-cyclohexylene or pyrimidine-2,5-diyl, or 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—, —COO—, —CH₂CH₂—, CH═CH—, or single bond.
 18. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH—, or single bond; and as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K represents trans-1,4-cyclohexylene or 1,4-phenylene group; and Z⁶ and Z⁷ independently represent —CH₂CH₂—, —CH₂O—, or single bond.
 19. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom; and ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom, and as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom; Z⁴ and Zr independently represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH—, or single bond.
 20. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents CN group or —C≡C—CN; ring D represents trans-1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene, 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom, or pyrimidine-2,5-diyl group; ring F represents trans-1,4-cyclohexylene or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; and a, b, and c are independently 0 or 1, and as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH—, or single bond.
 21. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-10, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom; and ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom, as a third component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents CN group or —C═C—CN; ring D represents trans-1,4-cyclohexylene, 1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene, 1,4-phenylene group hydrogen atom of which may be replaced by fluorine atom, or pyrimidine-2,5-diyl group; ring F represents trans-1,4-cyclohexylene or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1, and as a fourth component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms one or more non-adjacent methylene groups in the alkyl group may be replaced by oxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring 1, and ring J independently represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene group at least one hydrogen atom of which may be replaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH—, or single bond. 